Anthranilic acid derivatives

ABSTRACT

The present invention relates to novel anthranilic acid derivatives of the general formula (I) 
                         
in which R 1 , R 2 , R 3 , R 4 , R 5 , Qx, A, Qy and n have the meanings given in the description, to their use as insecticides and acaricides for controlling animal pests, also in combination with other agents for activity boosting, and to a plurality of processes for their preparation.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to EP 10166062.9 filed Jun. 15, 2010and U.S. Provisional Application No. 61/354,895 filed Jun. 15, 2010, thecontents of which are incorporated herein by reference in theirentireties.

BACKGROUND

1. Field of the Invention

The present invention relates to novel anthranilic acid derivatives, totheir use as insecticides and acaricides for controlling animal pests,also in combination with other agents for activity boosting, and to aplurality of processes for their preparation.

2. Description of Related Art

Anthranilic acid derivatives having insecticidal properties have alreadybeen described in the literature, as for example in WO 01/70671, WO03/015519, WO 03/016284, WO 03/015518, WO 03/024222, WO 03/016282, WO03/016283, WO 03/062226, WO 03/027099, WO 04/027042, WO 04/033468, WO2004/046129, WO 2004/067528, WO 2005/118552, WO 2005/077934, WO2005/085234, WO 2006/023783, WO 2006/000336, WO 2006/040113, WO2006/111341, WO 2007/006670, WO 2007/024833, WO2007/020877, WO2007/144100, WO2007/043677, WO2008/126889, WO2008/126890 andWO2008/126933.

In their application, however, the active compounds already known inaccordance with the specifications identified above have disadvantagesin some respects, whether it be that they exhibit a narrow spectrum ofapplication or whether it be that they do not have satisfactoryinsecticidal or acaricidal activity.

SUMMARY

Novel anthranilic acid derivatives have now been found which haveadvantages over the compounds already known, examples being betterbiological or environmental properties, broader application methods, animproved insecticidal or acaricidal activity, and also highcompatibility with useful plants. The anthranilic acid derivatives canbe used in combination with other agents for improving the efficacy inparticular against insects which are difficult to control.

The present invention accordingly provides novel anthranilic acidderivatives of the formula (I)

in which

-   R¹ represents hydrogen, amino, hydroxyl or represents C₁-C₆-alkyl,    C₂-C₆-alkenyl, C₂-C₆-alkynyl or C₃-C₆-cycloalkyl, each of which is    optionally mono- or polysubstituted by identical or different    substituents, where the substituents independently of one another    may be selected from the group consisting of halogen, cyano, nitro,    hydroxyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,    C₁-C₄-alkylsulphonyl, (C₁-C₄-alkoxy)carbonyl, C₁-C₄-alkylamino,    di-(C₁-C₄-alkyl)amino, C₃-C₆-cycloalkylamino and    (C₁-C₄-alkyl)-C₃-C₆-cycloalkylamino,-   R² represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,    di-(C₁-C₄-alkyl)amino, C₃-C₆-cycloalkylamino, C₁-C₆-alkoxycarbonyl    or C₁-C₆-alkylcarbonyl,-   R³ represents hydrogen or represents optionally mono- or    polysubstituted C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₃-C₆-cycloalkyl, where the substituents are    identical or different and independently of one another may be    selected from the group consisting of halogen, cyano, (C═O)OH,    (C═O)NH₂, nitro, hydroxyl, C₁-C₆-alkyl, C₃-C₆-cycloalkyl,    C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₂-C₆-alkoxycarbonyl,    C₂-C₆-alkylcarbonyl, C₃-C₆-trialkylsilyl or represents a phenyl ring    or a 5- or 6-membered unsaturated, partially saturated or saturated    heterocycle, where the phenyl ring or heterocycle is optionally    mono- or polysubstituted by identical or different substituents and    where the substituents independently of one another may be selected    from the group consisting of hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl,    C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl, halogen, CN, (C═O)OH,    (C═O)NH₂, NO₂, hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl,    C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino,    C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl,    (C₁-C₆-alkoxy)carbonyl, (C₁-C₆-alkyl)aminocarbonyl,    di-(C₁-C₄-alkyl)aminocarbonyl, tri-(C₁-C₂)alkylsilyl,    (C₁-C₄-alkyl)(C₁-C₄-alkoxy)imino, or-   R³ represents C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylcarbonyl,    C₁-C₆-alkylaminocarbonyl or di(C₁-C₆)alkylaminocarbonyl, or-   R³ represents a phenyl ring or a 5- or 6-membered unsaturated,    partially saturated or saturated heterocycle, where the phenyl ring    or heterocycle is optionally mono- or polysubstituted by identical    or different substituents and where the substituents independently    of one another may be selected from the group consisting of    hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl,    C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl, halogen, CN, (C═O)OH,    (C═O)NH₂, NO₂, OH, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl,    C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino, C₃-C₆-cycloalkylamino,    (C₁-C₆-alkyl)carbonyl, (C₁-C₆-alkoxy)carbonyl,    (C₁-C₆-alkyl)aminocarbonyl, di-(C₁-C₄-alkyl)aminocarbonyl,    tri-(C₁-C₂)alkylsilyl, (C₁-C₄-alkyl)(C₁-C₄-alkoxy)imino, or-   R² and R³ may be joined to one another via two to six carbon atoms    and form a ring which optionally additionally contains a further    nitrogen, sulphur or oxygen atom and may optionally be mono- to    tetrasubstituted by C₁-C₂-alkyl, C₁-C₂-haloalkyl, halogen, cyano,    amino C₁-C₂-alkoxy or C₁-C₂-haloalkoxy,-   R², R³ furthermore together represent ═S(C₁-C₄-alkyl)₂,    ═S(O)(C₁-C₄-alkyl)₂,-   R⁴ represents hydrogen, halogen, cyano, nitro, hydroxyl, amino,    carboxyl, OCN, SCN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₆-alkenyl,    C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy,    C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-haloalkoxy, SF₅, C₁-C₄-alkylthio,    C₁-C₄-alkylthio-C₁-C₄-alkyl, C₁-C₄-alkylsulphinyl,    C₁-C₄-alkylsulphonyl, C₁-C₄-alkylsulphonyloxy, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl,    C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino, C₁-C₄-alkylcarbonylamino,    N-methoxy-N-methylamino, C₁-C₄-alkoxycarbonyl,    C₁-C₄-alkoxycarbonyl-C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl,    C₁-C₄-alkylcarbonyloxy, aminocarbonyl, C₁-C₄-alkylaminocarbonyl,    C₁-C₄-dialkylaminocarbonyl, aminothiocarbonyl,    C₁-C₄-alkylaminothiocarbonyl, C₁-C₄-dialkylaminothiocarbonyl,    C₃-C₆-cycloalkylamino, (C₁-C₄-alkoxy)imino,    (C₁-C₄-alkyl)(C₁-C₄-alkoxy)imino,    (C₁-C₄-haloalkyl)(C₁-C₄-alkoxy)imino, C₁-C₄-alkylsulphonylamino,    aminosulphonyl, C₁-C₄-alkylaminosulphonyl,    C₁-C₄-dialkylaminosulphonyl, C₁-C₄-alkylsulphoximino,    C₃-C₆-trialkylsilyl or represents a 3- to 6-membered saturated,    partially saturated or aromatic ring which may optionally contain    one to three heteroatoms from the group consisting of O, S and N and    which may optionally be mono- or polysubstituted by identical or    different substituents from the group consisting of halogen, cyano,    nitro, hydroxyl, amino, carboxyl, C₁-C₄-alkyl, C₁-C₄-haloalkyl,    C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,    C₁-C₄-alkylsulphonyl, C₁-C₄-alkylsulphonyloxy, C₁-C₄-haloalkylthio,    C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl,    C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino, C₁-C₄-alkylcarbonylamino,    C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy,    aminocarbonyl, C₁-C₄-alkylaminocarbonyl, C₁-C₄-dialkylaminocarbonyl,    aminothiocarbonyl, C₁-C₄-alkylaminothiocarbonyl,    C₁-C₄-dialkylaminothiocarbonyl, C₃-C₆-cycloalkylamino,    C₁-C₄-alkylsulphonylamino, aminosulphonyl, C₁-C₄-alkylaminosulphonyl    and C₁-C₄-dialkylaminosulphonyl,

two radicals R⁴ form, via adjacent carbon atoms, a ring which represents—(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH═CH—)₂—, —OCH₂O—, —O—(CH₂)₂—, —OCF₂O—,—(CF₂)₂—, —O(CF₂)₂—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—, or

two radicals R⁴ furthermore form, via adjacent carbon atoms, the fusedrings below which are optionally mono- or polysubstituted by identicalor different substituents, where the substituents independently of oneanother may be selected from the group consisting of hydrogen, cyano,C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₃-C₆-halocycloalkyl,halogen, C₁-C₆-alkoxy, C₁-C₄-alkylthio(C₁-C₆-alkyl),C₁-C₄-alkylsulphinyl(C₁-C₆-alkyl), C₁-C₄-alkylsulphonyl(C₁-C₆-alkyl),C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino and C₃-C₆-cycloalkylamino,

n represents 0 to 3,

R⁵ represents C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl,C₁-C₆-halocycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₂-C₆-alkynyl,C₂-C₆-haloalkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, halogen, cyano,nitro or C₃-C₆-trialkylsilyl,

Q_(X) represents an aromatic or heteroaromatic 5- or 6-membered ringwhich may contain 1-3 heteroatoms from the group consisting of N, S, Oand which is optionally mono- or polysubstituted by identical ordifferent R⁷ substituents, where the radical R7 is attached via carbonif the ring is five-membered and contains exactly two nitrogen atomswhich are adjacent,

A represents optionally mono- or polysubstituted —(C₁-C₆-alkylene)-,—(C₂-C₆-alkenylene)-, —(C₂-C₆-alkynylene)-, —R⁸—(C₃-C₆-cycloalkyl)-R⁸—,—R⁸—O—R⁸—, —R⁸—S—R⁸—, —R⁸—S(═O)—R⁸—, —R⁸—S(═O)₂—R⁸—,—R⁸—N(C₁-C₆-alkyl)-R⁸—, R⁸—C═NO(C₁-C₆-alkyl)-R⁸, —CH[CO₂(C₁-C₆-alkyl)-,—R⁸—C(═O)—R⁸, —R⁸—C(═O)NH—R⁸, R⁸—C(═O)N(C₁-C₆-alkyl)-R⁸,—R⁸—C(═O)NHNH—R⁸—, —R⁸—C(═O)N(C₁-C₆-alkyl)-NH—R⁸—,—R⁸—C(═O)NHN(C₁-C₆-alkyl)-R⁸, —R⁸—O(C═O)—R⁸, —R⁸—O(C═O)NH—R⁸,—R⁸—O(C═O)N(C₁-C₆-alkyl)-R⁸, —R⁸—S(═O)₂NH—R⁸,—R⁸—(═O)₂N(C₁-C₆-alkyl)-R⁸, —R⁸—S(C═O)—R⁸, —R⁸—S(C═O)NH—R⁸,—R⁸—S(C═O)N(C₁-C₆-alkyl)-R⁸, —R⁸—NHNH—R⁸, —R⁸—NHN(C₁-C₆-alkyl)-R⁸,—R⁸—N(C₁-C₆-alkyl)-NH—R⁸, —R⁸—N(C₁-C₆-alkyl)-N(C₁-C₆-alkyl)-R⁸,—R⁸—N═CH—O—R⁸, —R⁸—NH(C═O)O—R⁸, —R⁸—N(C₁-C₆-alkyl)-(C═O)O—R⁸,—R⁸—NH(C═O)NH—R⁸, —R⁸—NH(C═S)NH—R⁸, —R⁸—NHS(═O)₂—R⁸, R⁸—NH—R⁸,R⁸—C(═O)—C(═O)—R⁸, R⁸—C(OH)—R⁸, R⁸—NH(C═O)—R⁸, R⁸-Qz-R⁸,R⁸—C(═N—NR′₂)—R⁸, R⁸—C(═C—R′₂)—R⁸ or —R⁸—N(C₁-C₆-alkyl)S(═O)₂—R⁸,

where the substituents independently of one another may be selected fromthe group consisting of halogen, cyano, nitro, hydroxyl, C1-C6-alkyl,C1-C6-alkyoxy, halo-C1-C6-alkyl, amino, (C1-C6-alkyl)amino,di(C₁-C₆-alkyl)amino, C3-C6-cyclo

where —(C₃-C₆-cycloalkyl)- in the ring may optionally contain 1 or 2heteroatoms selected from the group consisting of N, S, O,

R⁸ represents straight-chain or branched —(C₁-C₆-alkylene)- orrepresents a direct bond,

where a plurality of R⁸ radicals independently of one another representstraight-chain or branched —(C₁-C₆-alkylene)- or represent a directbond,

for example, R⁸—O—R⁸— represents —(C₁-C₆-alkylene)-O—(C₁-C₆-alkylene)-,—(C₁-C₆-alkylene)-O—, —O—(C₁-C₆-alkylene)-, or —O—,

where R′ represents alkyl, alkylcarbonyl, alkenyl, alkynyl which mayoptionally be mono- or polysubstituted by halogen,

Qz represents a 3- or 4-membered partially saturated or saturated ringor a 5- or 6-membered partially saturated, saturated or aromatic ring orrepresents a 6- to 10-membered bicyclic ring system,

where the ring or the bicyclic ring system may optionally contain 1-3heteroatoms from the group consisting of N, S, O,

where the ring or the bicyclic ring system is optionally mono- orpolysubstituted by identical or different substituents, and where thesubstituents independently of one another may be selected from the groupconsisting of hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, CONH₂, NO₂, OH, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino,C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl, (C₁-C₆-alkoxy)carbonyl,(C₁-C₆-alkyl)aminocarbonyl, di-(C₁-C₄-alkyl)aminocarbonyl,

Q_(Y) represents a 5- or 6-membered partially saturated or saturatedheterocyclic or heteroaromatic ring or an aromatic 8-, 9- or 10-memberedfused heterobicyclic ring system, where the ring or the ring system isoptionally mono- or polysubstituted by identical or differentsubstituents, and where the substituents independently of one anothermay be selected from the group consisting of hydrogen, C₁-C₆-alkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl,C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl, halogen, CN,CO₂H, CONH₂, NO₂, OH, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,C₁-C₄-halo, C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino,di-(C₁-C₄-alkyl)amino, C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl,(C₁-C₆-alkoxy)carbonyl, (C₁-C₆-alkyl)amino carbonyl,di-(C₁-C₄-alkyl)aminocarbonyl, tri-(C₁-C₂)alkylsilyl,(C₁-C₄-alkyl)(C₁-C₄-alkoxy)imino,

or where the substituents independently of one another may be selectedfrom the group consisting of phenyl and a 5- or 6-memberedheteroaromatic ring, where phenyl or the ring may optionally be mono- orpolysubstituted by identical or different substituents from the groupconsisting of C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, NO₂, OH, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy,

R⁷ represents hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₃-C₆-cycloalkoxyor

R⁹ independently represents hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₁-C₆-haloalkyl, halogen, cyano, nitro, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio or C₁-C₄-haloalkylthio,

p represents 0 to 4,

Z represents N, CH, CF, CCl, CBr or CI,

the compounds of the general formula (I) furthermore comprise N-oxidesand salts.

If appropriate, the compounds of the formula (I) may be present invarious polymorphic forms or as mixtures of different polymorphic forms.Both the pure polymorphs and the polymorph mixtures are provided by theinvention and can be used according to the invention.

The compounds of the formula (I) optionally include diastereomers orenantiomers.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

The formula (I) provides a general definition of the compounds accordingto the invention. Preferred, particularly preferred and veryparticularly preferred are compounds of the formula (I) in which

R1 preferably represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl,C2-C6-alkynyl, C3-C6-cycloalkyl, cyano(C1-C6-alkyl), C1-C6-haloalkyl,C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C1-C4-alkoxy-C1-C4-alkyl,C₁-C₄-alkylthio-C₁-C₄-alkyl, C1-C4-alkylsulphinyl-C₁-C₄-alkyl orC₁-C₄-alkylsulphonyl-C₁-C₄-alkyl,

R¹ particularly preferably represents hydrogen, methyl, ethyl,cyclopropyl, cyanomethyl, methoxymethyl, methylthiomethyl,methylsulphinylmethyl or methylsulphonylmethyl,

R¹ very particularly preferably represents hydrogen,

R² preferably represents hydrogen or C₁-C₆-alkyl.

R² particularly preferably represents hydrogen or methyl.

R² very particularly preferably represents hydrogen,

R³ preferably represents hydrogen or represents in each case optionallymono- or polysubstituted C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl,C₂-C₆-alkynyl, C₃-C₆-cycloalkyl, where the substituents are identical ordifferent and independently of one another may be selected from thegroup consisting of halogen, cyano, (C═O)OH, (C═O)NH₂, nitro, hydroxyl,C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl,C₂-C₆-alkoxycarbonyl, C₂-C₆-alkylcarbonyl or represents a phenyl ring ora 5- or 6-membered unsaturated, partially saturated or saturatedheterocycle, where the phenyl ring or heterocycle is optionally mono- orpolysubstituted by identical or different substituents and where thesubstituents independently of one another may be selected from the groupconsisting of hydrogen, C₁-C₆alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, (C═O)OH, (C═O)NH₂, NO₂, hydroxyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino,C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl, (C₁-C₆-alkoxy)carbonyl, or

R³ preferably represents C₂-C₄-alkoxycarbonyl, C₂-C₄-alkylcarbonyl,C₂-C₄-alkylaminocarbonyl or C₂-C₄-dialkylaminocarbonyl, or

R³ preferably represents a phenyl ring or a 5- or 6-memberedunsaturated, partially saturated or saturated heterocycle, where thephenyl ring or heterocycle is optionally mono- or polysubstituted byidentical or different substituents and where the substituentsindependently of one another may be selected from the group consistingof hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, (C═O)OH, (C═O)NH₂, NO₂, OH,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino,C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl, (C₁-C₆-alkoxy)carbonyl,

R³ particularly preferably represents hydrogen or represents in eachcase optionally mono- or polysubstituted C₁-C₆-alkyl, C₁-C₆-alkoxy orC₃-C₆-cycloalkyl, where the substituents are identical or different andindependently of one another may be selected from the group consistingof halogen, cyano, (C═O)OH, (C═O)NH₂, nitro, hydroxyl, C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₂-C₆-alkoxycarbonyl,C₂-C₆-alkylcarbonyl or represents a phenyl ring or a 5- or 6-memberedunsaturated, partially saturated or saturated heterocycle, where thephenyl ring or heterocycle is optionally mono- or polysubstituted byidentical or different substituents and where the substituentsindependently of one another may be selected from the group consistingof hydrogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl,C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl, halogen, CN,hydroxyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino,di-(C₁-C₄-alkyl)amino, C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl,(C₁-C₆-alkoxy)carbonyl or

R³ particularly preferably represents C₂-C₄-alkoxycarbonyl,C₂-C₄-alkylcarbonyl, C₂-C₄-alkylaminocarbonyl, or

R³ particularly preferably represents a phenyl ring or a 5- or6-membered unsaturated, partially saturated or saturated heterocycle,where the phenyl ring or heterocycle is optionally mono- orpolysubstituted by identical or different substituents and where thesubstituents independently of one another may be selected from the groupconsisting of hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, (C═O)NH₂, NO₂, OH, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,C₁-C₄-haloalkylsulphonyl, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino,C₃-C₆-cycloalkylamino, (C₁-C₆-alkyl)carbonyl, (C₁-C₆-alkoxy)carbonyl, or

R³ very particularly preferably represents hydrogen, C₁-C₄-alkyl(methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl ortert-butyl), cyclopropyl, cyclobutyl, cyano-C₁-C₃-alkyl (cyanomethyl,1-cyanoethyl, 2-cyanoethyl, 1-cyano-n-propyl, 2-cyano-n-propyl,3-cyano-n-propyl, 1-cyanoisopropyl, 2-cyanoisopropyl), phenyl, pyridyl,or

R³ especially preferably represents hydrogen, methyl, isopropyl,cyclopropyl, tert-butyl or cyanomethyl.

R⁴ preferably represents hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio orC₁-C₄-haloalkylthio,

two adjacent radicals R⁴ likewise preferably represent —(CH₂)₃—,—(CH₂)₄—, —(CH₂)₅—, —(CH—CH—)₂—, —OCH₂O—, —O(CH₂)₂O—, —OCF₂O—,—(CF₂)₂O—, —O(CF₂)₂O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,

R⁴ particularly preferably represents hydrogen, C₁-C₄-alkyl,C₁-C₂-haloalkyl, halogen, cyano or C₁-C₂-haloalkoxy,

two adjacent radicals R⁴ particularly preferably represent —(CH₂)₄—,—(CH═CH—)₂—, —O(CH₂)₂O—, —O(CF₂)₂O—, —(CH═CH—CH═N)— or —(CH═CH—N═CH)—,

R⁴ very particularly preferably represents hydrogen, methyl,trifluoromethyl, cyano, fluorine, chlorine, bromine, iodine ortrifluoromethoxy. Moreover, two adjacent radicals R⁴ very particularlypreferably represent —(CH₂)₄— or —(CH═CH—)₂—.

R⁴ especially preferably represents chlorine, fluorine or bromine,

R⁴ furthermore especially preferably represents iodine or cyano.

two adjacent radicals R⁴ especially preferably represent —(CH═CH—)₂

R⁵ preferably represents C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl,C₁-C₆-halocycloalkyl, C₂-C₆-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl,C₂-C₄-haloalkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio,C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, halogen, cyano,nitro or C₃-C₆-trialkylsilyl,

R⁵ particularly preferably represents C₁-C₄-alkyl, C₃-C₆-cycloalkyl,C₁-C₄-haloalkyl, C₁-C₆-halocycloalkyl, C₂-C₆-alkenyl, C₂-C₄-haloalkenyl,C₂-C₄-alkynyl, C₂-C₄-haloalkynyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,fluorine, chlorine, bromine, iodine, cyano, nitro orC₃-C₆-trialkylsilyl,

R⁵ very particularly preferably represents methyl, fluorine, chlorine,bromine or iodine,

R⁵ especially preferably represents methyl or chlorine,

Q_(X) preferably represents a heteroaromatic 5-membered ring which maycontain 1-3 heteroatoms from the group consisting of N, S, O and whichis optionally mono- or polysubstituted by identical or different R⁷substituents, where the radical R⁷ is attached via carbon if the ring isfive-membered and contains exactly two nitrogen atoms which areadjacent,

or represents a heteroaromatic 6-membered ring which may contain 1-3nitrogen atoms, or represents phenyl,

Q_(X) particularly preferably represents a 5- or 6-membered ring whichis optionally mono- or polysubstituted by identical or different R⁷substituents and is selected from the group consisting of furan,thiophene, triazole, imidazole, thiazole, oxazole, isoxazole,isothiazole, thiadiazole, oxadiazole, pyrrole, pyridine, pyrimidine,pyridazine, pyrazine, phenyl or represents pyrazole where the radical R⁷is attached via carbon to the pyrazole,

Q_(X) very particularly preferably represents thiazole, oxazole,pyrrole, imidazole, triazole, pyrimidine, phenyl or represents pyrazolewhere the radical R⁷ is attached via carbon to the pyrazole,

which is monosubstituted by the group R⁷

where Z, R and p may have the general meanings given above or thepreferred or particularly preferred meanings given below,

A preferably represents optionally mono- or polysubstituted—(C₁-C₄alkylene)-, —(C₂-C₄-alkenylene)-, —(C₂-C₄-alkynylene)-,—R⁸—(C₃-C₆-cycloalkyl)-R⁸—, —R⁸—O—R⁸—, —R⁸—S—R⁸—, —R⁸—S(═O)—R⁸—,—R⁸—S(═O)₂—R⁸—, —R⁸—C═NO(C₁-C₄-alkyl), —R⁸—C(═O)—R⁸, —R⁸—C(═S)—R⁸,—R⁸—C(═O)NH—R⁸, R⁸—C(═O)N(C₁-C₄-alkyl)-R⁸, —R⁸—S(═O)₂NH—R⁸,—R⁸—S(═O)₂N(C₁-C₄-alkyl)-R⁸, —R⁸—NH(C═O)O—R⁸,—R⁸—N(C₁-C₄-alkyl)-(C═O)O—R⁸, —R⁸—NH(C═O)NH—R⁸, —R⁸—NHS(═O)₂—R⁸,—R⁸—N(C₁-C₄-alkyl)S(═O)₂—R⁸, R⁸—NH—R⁸, R⁸C(═O)—C(═O)—R⁸, R⁸C(OH)—R⁸,R⁸-Qz-R⁸,

where the substituents independently of one another may be selected fromthe group consisting of halogen, cyano, nitro, hydroxyl, C₁-C₆-alkyl,C₁-C₆-alkyoxy and halo-C₁-C₆-alkyl,

where Qz may have the general meanings given above or the preferred orparticularly preferred meanings given below,

A particularly preferably represents —CH₂—, —CH₂O—, —CH₂OCH₂—, —CH₂S—,—CH₂SCH₂—, —CH₂N(C₁-C₄-alkyl)-, —CH₂N(C₁-C₄-alkyl)CH₂—, —CH(Hal)-,—C(Hal)₂-, —CH(CN)—, CH₂(CO)—, CH₂(CS)—, CH₂CH(OH)—, -cyclopropyl-,CH₂(CO)CH₂—, —CH(C₁-C₄-alkyl)-, —C(di-C₁-C₆-alkyl)-, —CH₂CH₂—, —CH═CH—,—C≡C—, —C═NO(C₁-C₆-alkyl), —C(═O)(C₁-C₄-alkyl)-,

A very particularly preferably represents —CH₂—, —CH(CH₃), C(CH₃)₂,—CH₂CH₂—, —CH(CN)—, —CH₂O— or —C(═O)—CH₂—,

A especially preferably represents CH₂, CH(CH₃), —CH₂O— or —C(═O)—CH₂—,

Qz preferably represents a 3- or 4-membered partially saturated orsaturated ring or represents a 5- or 6-membered partially saturated,saturated or aromatic ring, where the ring may optionally contain 1-3heteroatoms from the group consisting of N, S, O,

where the ring is optionally mono- or polysubstituted by identical ordifferent substituents and where the substituents independently of oneanother may be selected from the group consisting of hydrogen,C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₆-cycloalkyl,C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, OH, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylthio, C₁-C₄-halo, C₁-C₄-haloalkylsulphonyl,

Qz particularly preferably represents a 3- to 4-membered, partiallysaturated or saturated ring or represents a 5-membered partiallysaturated, saturated or aromatic ring, where the ring may optionallycontain 1-2 heteroatoms from the group consisting of N, S, O,

where the ring is optionally mono- or polysubstituted by identical ordifferent substituents and where the substituents independently of oneanother may be selected from the group consisting of hydrogen,C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₆-cycloalkyl,C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, OH, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl,

Qz very particularly preferably represents azetidine, oxetane orthietane, pyrrolidine, pyrroline, pyrazolidine, pyrazoline,imidazolidine, imidazolidone, imidazoline, tetrahydrofuran,tetrahydrothiophene, thiazolidine, isothiazolidine, isoxazoline,

which are optionally mono- or polysubstituted by identical or differentsubstituents, where the substituents independently of one another may beselected from the group consisting of hydrogen, methyl, ethyl,isopropyl, hydroxyl, methoxy, trifluoromethoxy, fluorine, chlorine,bromine, cyano, difluoromethyl, trifluoromethyl,

R⁷ preferably represents C₁-C₆-alkyl or represents the radical

R⁷ furthermore preferably represents C₃-C₆-cycloalkoxy,

R⁷ particularly preferably represents methyl or represents the radical

R⁹ independently preferably represents hydrogen, halogen, cyano,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy,C₁-C₄-haloalkylsulphonyl or (C₁-C₄-alkyl)-C₁-C₄-alkoxyimino,

R⁹ independently particularly preferably represents hydrogen, halogen,CN or C₁-C₄-haloalkyl,

R⁹ independently very particularly preferably represents fluorine,chlorine or bromine,

R⁹ especially preferably represents chlorine,

p preferably represents 1, 2 or 3,

p particularly preferably represents 1 or 2,

p very particularly preferably represents 1,

Z preferably represents N, CH, CF, CCl, CBr or CI,

Z particularly preferably represents N, CH, CF, CCl or CBr,

Z very particularly preferably represents N, CCl or CH,

R⁸ preferably represents straight-chain or branched —(C₁-C₄-alkylene)-or represents a direct bond

R⁸ particularly preferably represents methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl or isobutyl or a direct bond

R⁸ very particularly preferably represents methyl or ethyl or a directbond

Q_(Y) preferably represents a 5- or 6-membered partially saturated orsaturated heterocyclic or heteroaromatic ring or an aromatic 8-, 9- or10-membered fused heterobicyclic ring system where the heteroatoms maybe selected from the group consisting of N, S, O, where the ring or thering system is optionally mono- or polysubstituted by identical ordifferent substituents and where the substituents independently of oneanother may be selected from the group consisting of hydrogen,C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₆-cycloalkyl,C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, CO₂H, CO₂NH₂, NO₂, OH, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl,C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,C₁-C₄-haloalkylsulphonyl,

or where the substituents independently of one another may be selectedfrom the group consisting of phenyl and a 5- or 6-memberedheteroaromatic ring, where phenyl or the ring may optionally be mono- orpolysubstituted by identical or different substituents from the groupconsisting of C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, NO₂, OH, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy,

Q_(Y) particularly preferably represents an optionally mono- orpolysubstituted 5- or 6-membered heteroaromatic ring from the groupconsisting of Q-1 to Q-53 and Q-58 to Q-59, Q62 to Q63, an aromatic9-membered fused heterobicyclic ring system Q-54 to Q-56 or a 5-memberedheterocyclic ring Q-60 to Q-61 where the substituents independently ofone another may be selected from the group consisting of C₁-C₃-alkyl,C₁-C₃-haloalkyl, C₁-C₂-alkoxy, halogen, cyano, hydroxyl, nitro andC₁-C₂-haloalkoxy,

or where the substituents independently of one another may be selectedfrom the group consisting of phenyl and a 5- or 6-memberedheteroaromatic ring, where phenyl or the ring may optionally be mono- orpolysubstituted by identical or different substituents from the groupconsisting of C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, NO₂, OH, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy,

Q_(Y) very particularly preferably represents an optionally mono- orpolysubstituted 5- or 6-membered heteroaromatic ring from the groupconsisting of Q-36 to Q-40, Q43, Q-58 to Q-59, Q62, Q63, an aromatic9-membered fused heterobicyclic ring system Q-54 to Q-56 or a 5-memberedheterocyclic ring Q-60 to Q-61 where the substituents independently ofone another may be selected from the group consisting of C₁-C₃-alkyl,C₁-C₃-haloalkyl, C₁-C₂-alkoxy, halogen, cyano, hydroxyl, nitro andC₁-C₂-haloalkoxy,

or where the substituents independently of one another may be selectedfrom the group consisting of phenyl and a 5- or 6-memberedheteroaromatic ring, where phenyl or the ring may optionally be mono- orpolysubstituted by identical or different substituents from the groupconsisting of C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl,C₃-C₆-halocycloalkyl, halogen, CN, NO₂, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,

Q_(Y) especially preferably represents an optionally mono- orpolysubstituted heteroaromatic ring from the group consisting of Q-37,Q-38, Q-39, Q-40, Q43, Q-58, Q-59, Q62 and Q63 or a 5-memberedheterocyclic ring Q-60 where the substituents are identical or differentand independently of one another may be selected from the groupconsisting of methyl, ethyl, cyclopropyl, tert-butyl, chlorine,fluorine, iodine, bromine, cyano, nitro, difluoromethyl,trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl andisoheptafluoropropyl

or where the substituents independently of one another may be selectedfrom the group consisting of phenyl and a 5- or 6-memberedheteroaromatic ring, where the substituents independently of one anothermay be selected from the group consisting of methyl, ethyl, cyclopropyl,tert-butyl, chlorine, fluorine, iodine, bromine, cyano, nitro,difluoromethyl, trifluoromethyl, pentafluorethyl, n-heptafluoropropyland isoheptafluoropropyl,

The rings or ring systems listed above may optionally independently ofone another additionally be substituted by oxo, thioxo, (═O)═NH,(═O)═N—CN, (═O)₂. Examples which may be mentioned aretetrahydrothiophene dioxide, imidazolidone.

In this case, the oxo group as substituent at a ring carbon atom means,for example, a carbonyl group in the heterocyclic ring. This alsopreferably comprises lactones and lactams. The oxo group may also bepresent at the hetero ring atoms, which may exist in various oxidationlevels, for example in the case of nitrogen and sulphur, in which casethey form, for example, the divalent groups —N(O)—, —S(O)— (alsoabbreviated as SO) and —S(O)₂— (also abbreviated as SO₂) in theheterocyclic ring. In the case of —N(O)— and —S(O)— groups, in each caseboth enantiomers are included.

In a heterocyclic ring, substituents other than the oxo group can alsobe attached to a heteroatom, for example a nitrogen atom, if a hydrogenatom at the nitrogen atom of the skeleton is replaced in the process. Inthe case of the nitrogen atom and also other heteroatoms such as, forexample, the sulphur atom, there may also be further substitution withformation of quaternary ammonium compounds or sulphonium compounds.

The above-recited general radical definitions and elucidations or thoserecited in preference ranges may be combined arbitrarily with oneanother, in other words including combinations between the respectiveranges and preference ranges. They apply both to the end products and,correspondingly, to precursors and intermediates.

Preference in accordance with the invention is given to the compounds ofthe formula (I) which contain a combination of the meanings listed aboveas being preferred (preferably).

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given tocompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

The compounds of the formulae (I) may be present more particularly inthe form of different regioisomers: for example in the form of mixturesof compounds where the attachment of the ring or the ring system Qy tothe radical (A) is in each case via different carbon or nitrogen atoms.

Furthermore, for example, in the form of mixtures of compounds havingthe definition Q62 and Q63, respectively, or in the form of mixtures ofcompounds having the definition Q58 and Q59. The invention thereforealso comprises mixtures of compounds of the formula (I) where QY has themeanings Q62 and Q63 and also Q58 and Q59 and the compounds may bepresent in various mixing ratios. Preference in this context is given tomixing ratios of the compounds of the formula (I) in which the radicalQY is Q62 or Q58 to compounds of the formula (I) in which the radical QYis Q63 or Q59, of 60:40 to 99:1, particularly preferably of 70:30 to98:2, very particularly preferably of 80:20 to 97:3. Especiallypreferred are the following mixing ratios for a compound of the formula(I) where QY has the definition Q62 or Q58 to the compound of theformula (I) where QY has the definition Q63 or Q59: 80:20; 81:19; 82:18;83:17; 84:16; 85:15, 86:14; 87:13; 88:12; 89:11; 90:10, 91:9; 92:8;93:7; 94:6; 95; 5; 96:4; 97:3.

Preparation Processes

The compounds of the general formula (I) can be obtained when

(A) anilines of the formula (II)

in which R¹, R², R³, R⁴, R⁵ and n have the meanings given above and Xrepresents O,

are reacted, for example, with carbonyl chlorides of the formula (III)

where

Qx, A and Qy have the meanings given above,

in the presence of an acid-binding agent; or

(B) anilines of the formula (II)

in which R¹, R², R³, R⁴, R⁵ and n have the meanings given above and Xrepresents O,

are reacted, for example, with a carboxylic acid of the formula (IV)

where

Qx, A and Qy have the meanings given above,

in the presence of a condensing agent; or

(C) for the synthesis of anthranilamides of the formula (I) in which R¹represents hydrogen,

for example, benzoxazinones of the formula (V)

in which R⁴, R⁵, Qx, A, Qy and n have the meanings given above

are reacted with an amine of the formula (VI)

in which R³ has the meanings given above

in the presence of a diluent to give compounds of the formula (I)according to the invention.

In particular, compounds of the general formula (I),

in which Qx represents

can be prepared when

(B-1) anilines of the formula (II)

in which R¹, R², R³, R⁴, R⁵ and n have the meanings given above

are reacted, for example, with a carboxylic acid of the formula (IV-1)

in which R⁷, A and Qy have the meanings given above,

in the presence of a condensing agent.

Carboxylic acids of the formula (IV-1) can be prepared according to thereaction scheme below in which R⁷, A, Qy have the meanings given aboveand R represents C₁-C₆-alkyl and Hal represents halogen from compoundsof the formula (VIII). Compounds of the formula (VIII) are known (forexample J. Med. Chem. 49, 2006, 4721-4736). The conversion of (VIII)into (IX) can be carried out by known methods (for exampleWO2005/113506). The further reaction via compounds of the formula X tocompounds of the formula (IV-1) can be carried out by known methods(e.g. WO2007/144100).

In particular, compounds of the general formula (I),

in which Qx represents

can be prepared when

(B-2) anilines of the formula (II)

in which R¹, R², R³, R⁴, R⁵, X and n have the meanings given above

are reacted, for example, with a carboxylic acid of the formula (IV-2)

in which R⁷, A and Qy have the meanings given above,

in the presence of a condensing agent.

Carboxylic acids of the formula (IV-2) can be prepared according to thereaction scheme below in which R⁷, A and Qy have the meanings givenabove and R represents C₁-C₆-alkyl and Hal represents halogen fromcompounds of the formula (XI). Compounds of the formula (XI) are known(for example J. Med. Chem. 49, 2006, 4721-4736). The conversion of (XI)into (XII) can be carried out by known methods (e.g. WO2005/113506). Thefurther reaction via XIII to carboxylic acids of the formula (IV-2) canbe carried out by known methods (for example WO2007/144100).

In particular, compounds of the general formula (I),

in which Qx represents

can be prepared by reacting

(B-3) anilines of the formula (II)

in which R1, R2, R3, R4, R5, X and n have the meanings given above

for example with a carboxylic acid of the formula (IV-3)

in which R⁷, A and Qy have the meanings given above,

in the presence of a condensing agent.

Carboxylic acids of the formula (IV-3) are novel. They can be preparedaccording to the reaction scheme below, where R⁷ and Q_(y) have themeanings given above and R represents C₁-C₆-alkyl, from compounds of theformula XIV. Compounds of the formula XIV are known (for example WO2003016283). The conversion of compounds of the formula XIV intocompounds of the formula XV can be carried out by known methods using,for example, (1-ethoxyvinyl)tributylstannane with palladium catalysis(for example J. Med. Chem. 41, 1998, 3736). The further conversion intocompounds of the formula XVI is carried out using a suitablehalogenating agent (for example Bioorganic & Medicinal ChemistryLetters, 19(4), 1199-1205; 2009). Coupling with Qy to give compounds ofthe formula XVII and hydrolysis to carboxylic acids of the formula IV-3are carried out by known methods (for example Bioorganic & MedicinalChemistry, 17(6), 2410-2422; 2009 and WO2006004903).

In particular, compounds of the general formula (I),

in which Qx represents

can be prepared when

(B-4) anilines of the formula (II)

in which R¹, R², R³, R⁴, R⁵, X and n have the meanings given above

are reacted for example with a carboxylic acid of the formula (IV-4)

in which R⁷, A and Qy have the meanings given above,

in the presence of a condensing agent.

Carboxylic acids of the formula (IV-4) can be prepared according to thereaction scheme below in which R7, A and Qy have the meanings givenabove and R represents C₁-C₆-alkyl and Hal represents halogen fromcompounds of the formula (XVIII) using (XIX). Compounds of the formula(XVIII) are known (for example WO 2007/043677) and commerciallyavailable. Compounds of the formula (XIX) are commercially available.The alkylation of (XVIII) with (XIX) can be carried out by known methods(for example Bioorg. Med. Chem. 2008, 16, 10165-10171). The furtherconversion of compounds of the formula (XX) into compounds of theformula (IV-4) can be carried out by known methods (for exampleWO2007/144100).

In particular, compounds of the general formula (I),

in which Qx represents

can be prepared when

(B-5) anilines of the formula (II)

in which R1, R2, R3, R4, R5, X and n have the meanings given above

are reacted for example with a carboxylic acid of the formula (IV-5)

in which R7, A and Qy have the meanings given above,

in the presence of a condensing agent.

Carboxylic acids of the formula (IV-5) can be prepared according to thereaction scheme below in which R7, A and Qy have the meanings givenabove and R represents C₁-C₆-alkyl and Hal represents halogen fromcompounds of the formula (XXI). Compounds of the formula (XXI) are knownand can be prepared by known methods (for example J. Med. Chem. 2006,49, 4721-4736). The conversion of (XXI) into (XXII) can be carried outby known methods (for example WO2005/113506). The further conversion via(XXIII) into carboxylic acids of the formula (IV-5) can be carried outby known methods (for example WO2007/144100).

The active compounds according to the invention, in combination withgood plant tolerance and favourable toxicity to warm-blooded animals andbeing tolerated well by the environment, are suitable for protectingplants and plant organs, for increasing the harvest yields, forimproving the quality of the harvested material and for controllinganimal pests, in particular insects, arachnids, helminths, nematodes andmolluscs, which are encountered in agriculture, in horticulture, inanimal husbandry, in forests, in gardens and leisure facilities, in theprotection of stored products and of materials, and in the hygienesector. They can preferably be used as crop protection compositions.They are active against normally sensitive and resistant species andagainst all or some stages of development. The abovementioned pestsinclude:

From the order of the Anoplura (Phthiraptera), for example, Damaliniaspp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectesspp.

From the class of the Arachnida, for example, Acarus siro, Aceriasheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp.,Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp.,Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri,Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp.,Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychusspp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp.,Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp.,Tarsonemus spp., Tetranychus spp., Vasates lycopersici.

From the class of the Bivalva, for example, Dreissena spp.

From the order of the Chilopoda, for example, Geophilus spp., Scutigeraspp.

From the order of the Coleoptera, for example, Acanthoscelides obtectus,Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis,Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp.,Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus,Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp.,Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchuslapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinuscubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans,Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosternaconsanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus,Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha,Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptushololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchussulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp.,Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinusspp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp.,Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor,Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrusspp.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata,Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp.,Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fanniaspp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp.,Liriomyza spp. Lucilia spp., Musca spp., Nezara spp., Oestrus spp.,Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanusspp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.

From the class of the Gastropoda, for example, Anion spp., Biomphalariaspp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp.,Oncomelania spp., Succinea spp.

From the class of the helminths, for example, Ancylostoma duodenale,Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp.,Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori,Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.,Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum,Dracunculus medinensis, Echinococcus granulosus, Echinococcusmultilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp.,Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa,Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocercavolvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp.,Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp.,Taenia saginata, Taenia solium, Trichinella spiralis, Trichinellanativa, Trichinella britovi, Trichinella nelsoni, Trichinellapseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereriabancrofti.

It is furthermore possible to control protozoa, such as Eimeria.

From the order of the Heteroptera, for example, Anasa tristis,Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida,Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis,Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistusspp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisaspp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae,Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp.,Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergellasingularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatomaspp.

From the order of the Homoptera, for example, Acyrthosipon spp.,Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobusbarodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui,Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis,Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani,Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicorynebrassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacunalanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii,Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola,Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp.,Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp.,Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccusspp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelisbilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterusarundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphaxstriatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi,Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari,Metcalfiella spp., Metopolophium dirhodum, Monellia costalis,Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettixspp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga,Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp.,Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodonhumuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp.,Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcusspp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp.,Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp.,Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus,Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina,Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp.,Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp.,Unaspis spp., Viteus vitifolii.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Isopoda, for example, Armadillidium vulgare,Oniscus asellus and Porcellio scaber.

From the order of the Isoptera, for example, Reticulitermes spp. andOdontotermes spp.

From the order of the Lepidoptera, for example, Acronicta major, Aedialeucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathrabrassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana,Capua reticulana, Carpocapsa pomonella, Chematobia brumata, Chilo spp.,Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Eariasinsulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp.,Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp.,Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella,Laphygma spp., Lithocolletis blancardella, Lithophane antennata,Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestrabrassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae,Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella,Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp.,Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesiagemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana,Trichoplusia spp.

From the order of the Orthoptera, for example, Acheta domesticus, Blattaorientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae,Locusta spp., Melanoplus spp., Periplaneta americana, Schistocercagregaria.

From the order of the Siphonaptera, for example, Ceratophyllus spp. andXenopsylla cheopis.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanoptera, for example, Baliothrips biformis,Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothripsfemoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothripsspp., Taeniothrips cardamoni and Thrips spp.

From the order of the Thysanura, for example, Lepisma saccharina.

The phytoparasitic nematodes include, for example, Anguina spp.,Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchusdipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp.,Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholussimilis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp.,Tylenchulus spp., Tylenchulus semipenetrans and Xiphinema spp.

The effectiveness of the compounds of the formula (I) can be increasedby adding ammonium salts and phosphonium salts. The ammonium salts andphosphonium salts are defined by formula (XI)

in which

D represents nitrogen or phosphorus,

D preferably represents nitrogen,

R¹⁰, R¹¹, R¹² and R¹³ independently of one another represent hydrogen orin each case optionally substituted C₁-C₈-alkyl or mono- orpolyunsaturated, optionally substituted C₁-C₈-alkylene where thesubstituents may be selected from the group consisting of halogen, nitroand cyano,

R¹⁰, R¹¹, R¹² and R¹³ preferably independently of one another representhydrogen or in each case optionally substituted C₁-C₄-alkyl, where thesubstituents may be selected from the group consisting of halogen, nitroand cyano,

R¹⁰, R¹¹, R¹² and R¹³ particularly preferably independently of oneanother represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl or t-butyl,

R¹⁰, R¹¹, R¹² and R¹³ very particularly preferably represent hydrogen,

m represents 1, 2, 3 or 4,

m preferably represents 1 or 2,

R¹⁴ represents an inorganic or organic anion,

R¹⁴ preferably represents bicarbonate, tetraborate, fluoride, bromide,iodide, chloride, monohydrogenphosphate, dihydrogenphosphate,hydrogensulphate, tartrate, sulphate, nitrate, thiosulphate,thiocyanate, formate, lactate, acetate, propionate, butyrate,pentanoate, citrate or oxalate,

R¹⁴ particularly preferably represents lactate, sulphate,monohydrogenphosphate, dihydrogenphosphate, nitrate, thiosulphate,thiocyanate, citrate, oxalate or formate,

R¹⁴ very particularly preferably represents sulphate.

The ammonium salts and phosphonium salts of the formula (XXIV) can beused in a wide concentration range for increasing the effect of cropprotection compositions comprising compounds of the formula (I). Ingeneral, the ammonium salts or phosphonium salts are used in theready-to-use crop protection composition in a concentration of from 0.5to 80 mmol/l, preferably 0.75 to 37.5 mmol/l, particularly preferably1.5 to 25 mmol/l. In the case of a formulated product, the concentrationof ammonium salt and/or phosphonium salt in the formulation is selectedsuch that it is within these stated general, preferred or particularlypreferred ranges following dilution of the formulation to the desiredactive compound concentration. The concentration of the salt in theformulation here is usually 1-50% by weight.

In one preferred embodiment of the invention, it is not an ammonium saltand/or phosphonium salt, but a penetrant, that is added to the cropprotection compositions to increase the activity. An activity increasecan be observed even in these cases. The present invention thus alsoprovides the use of a penetrant, and also the use of a combination ofpenetrant and ammonium salts and/or phosphonium salts for increasing theactivity of crop protection compositions which compriseacaricidally/insecticidally active compounds of the formula (I) asactive compound. Finally, the invention also provides the use of thesecompositions for controlling harmful insects.

Suitable penetrants in the present context are all those substanceswhich are usually used for improving the penetration of agrochemicalactive compounds into plants. Penetrants are defined in this context bytheir ability to penetrate from the aqueous spray liquor and/or from thespray coating into the cuticle of the plant and thereby increase themobility of active compounds in the cuticle. The method described in theliterature (Baur et al., 1997, Pesticide Science 51, 131-152) can beused for determining this property.

Suitable penetrants are, for example, alkanol alkoxylates. Penetrantsaccording to the invention are alkanol alkoxylates of the formulaR—O-(-AO)_(v)—R′  (XXV)in which

R represents straight-chain or branched alkyl having 4 to 20 carbonatoms

R′ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, n-pentyl or n-hexyl,

AO represents an ethylene oxide radical, a propylene oxide radical, abutylene oxide radical or represents mixtures of ethylene oxide andpropylene oxide radicals or butylene oxide radicals and

v represents a number from 2 to 30.

A preferred group of penetrants are alkanol alkoxylates of the formulaR—O-(-EO—)n-R′  (XXV-a)

in which

R has the meaning given above,

R′ has the meaning given above,

EO represents —CH2—CH2—O— and

n represents a number from 2 to 20.

A further preferred group of penetrants are alkanol alkoxylates of theformulaR—O-(-EO—)_(p)-(—PO—)_(q)-R′  (XXV-b)in which

R has the meaning given above,

R′ has the meaning given above,

EO represents —CH2—CH2—O—,

PO represents

p represents a number from 1 to 10 and

q represents a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of theformulaR—O-(—PO—)r-(EO—)s-R′  (XXV-c)

in which

R has the meaning given above,

R′ has the meaning given above,

EO represents —CH2—CH2—O—,

PO represents

r represents a number from 1 to 10 and

s represents a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of theformulaR—O-(-EO—)_(p)-(-BO—)_(q)-R′  (XXV-d)in which

R and R′ have the meanings given above,

EO represents —CH2—CH2—O—,

BO represents

p represents a number from 1 to 10 and

q represents a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of theformulaR—O-(-BO—)_(r)-(-EO—)_(s)-R′  (XXV-e)in which

R and R′ have the meanings given above,

BO represents

EO represents —CH2—CH2—O—,

r represents a number from 1 to 10 and

s represents a number from 1 to 10.

A further preferred group of penetrants are alkanol alkoxylates of theformulaCH₃—(CH₂)_(t)—CH₂—O—(—CH₂—CH₂—O—)_(u)—R′  (XXV-f)in which

R′ has the meaning given above,

t represents a number from 8 to 13.

y represents a number from 6 to 17.

In the formulae given above,

R preferably represents butyl, isobutyl, n-pentyl, isopentyl, neopentyl,n-hexyl, isohexyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl,decyl, n-dodecyl, isododecyl, lauryl, myristyl, isotridecyl,trimethylnonyl, palmityl, stearyl or eicosyl.

As an example of an alkanol alkoxylate of the formula (XXV-c), mentionmay be made of 2-ethylhexyl alkoxylate of the formula

in which

EO represents —CH2—CH2—O—,

PO represents

and

the numbers 8 and 6 represent average values.

As an example of an alkanol alkoxylate of the formula (XII-d), mentionmay be made of the formulaCH₃—(CH₂)₁₀—O-(-EO—)₆-(-BO—)₂-CH₃  (XXV-d-1)in which

EO represents —CH2—CH2—O—,

BO represents

and

the numbers 10, 6 and 2 represent average values.

Particularly preferred alkanol alkoxylates of the formula (XXV-f) arecompounds of this formula in which

t represents a number from 9 to 12 and

u represents a number from 7 to 9.

With very particular preference, mention may be made of alkanolalkoxylate of the formula (XXV-f-1)CH₃—(CH₂)_(t)—CH₂—O—(—CH₂—CH₂—O—))_(u)-R′  (XXV-f-1)in which

t represents the average value 10.5 and

u represents the average value 8.4.

The above formulae provide general definitions of the alkanolalkoxylates. These substances are mixtures of substances of the statedtype with different chain lengths. The indices are therefore averagevalues which may also deviate from whole numbers.

The alkanol alkoxylates of the stated formulae are known, and some ofthem are commercially available or can be prepared by known methods (cf.WO 98/35 553, WO 00/35 278 and EP-A 0 681 865)

Suitable penetrants also include, for example, substances which promotethe solubility of the compounds of the formula (I) in the spray coating.These include, for example, mineral and vegetable oils. Suitable oilsare all mineral or vegetable oils—modified or otherwise—which canusually be used in agrochemical compositions. By way of example, mentionmay be made of sunflower oil, rapeseed oil, olive oil, castor oil, colzaoil, maize seed oil, cottonseed oil and soybean oil or the esters ofsaid oils. Preference is given to rapeseed oil, sunflower oil and theirmethyl or ethyl esters.

The concentration of penetrant can be varied within a wide range. In thecase of a formulated crop protection composition, it is generally 1 to95% by weight, preferably 1 to 55% by weight, particularly preferably15-40% by weight. In the ready-to-use compositions (spray liquors), theconcentrations are generally between 0.1 and 10 g/l, preferably between0.5 and 5 g/l.

Inventively emphasized combinations of active compound, salt andpenetrant are listed in the table below. Here, “according to test” meansthat any compound which acts as penetrant in the cuticle penetrationtest (Baur et al., 1997, Pesticide Science 51, 131-152) is suitable.

Active # com- pound Salt Penetrant 1 I ammonium sulphate according totest 2 I ammonium lactate according to test 3 I ammonium nitrateaccording to test 4 I ammonium thiosulphate according to test 5 Iammonium thiocyanate according to test 6 I ammonium citrate according totest 7 I ammonium oxalate according to test 8 I ammonium formateaccording to test 9 I ammonium hydrogenphosphate according to test 10 Iammonium dihydrogenphosphate according to test 11 I ammonium carbonateaccording to test 12 I ammonium benzoate according to test 13 I ammoniumsulphite according to test 14 I ammonium benzoate according to test 15 Iammonium hydrogenoxalate according to test 16 I ammonium hydrogencitrateaccording to test 17 I ammonium acetate according to test 18 Itetramethylammonium sulphate according to test 19 I tetramethylammoniumlactate according to test 20 I tetramethylammonium nitrate according totest 21 I tetramethylammonium thiosulphate according to test 22 Itetramethylammonium thiocyanate according to test 23 Itetramethylammonium citrate according to test 24 I tetramethylammoniumoxalate according to test 25 I tetramethylammonium formate according totest 26 I tetramethylammonium hydrogenphosphate according to test 27 Itetramethylammonium according to test dihydrogenphosphate 28 Itetraethylammonium sulphate according to test 29 I tetraethylammoniumlactate according to test 30 I tetraethylammonium nitrate according totest 31 I tetraethylammonium thiosulphate according to test 32 Itetraethylammonium thiocyanate according to test 33 I tetraethylammoniumcitrate according to test 34 I tetraethylammonium oxalate according totest 35 I tetraethylammonium formate according to test 36 Itetraethylammonium hydrogenphosphate according to test 37 Itetraethylammonium dihydrogenphosphate according to test

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides,safeners, growth regulators or agents to improve plant properties, or asmicrobicides, for example as fungicides, antimycotics, bactericides,viricides (including agents against viroids) or as agents against MLO(mycoplasma-like organisms) and RLO (rickettsia-like organisms). Ifappropriate, they can also be used as intermediates or precursors forthe synthesis of other active compounds.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, water- and oil-basedsuspensions, powders, dusts, pastes, soluble powders, soluble granules,granules for broadcasting, suspoemulsion concentrates, natural compoundsimpregnated with active compound, synthetic substances impregnated withactive compound, fertilizers and also microencapsulations in polymericsubstances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, i.e. liquid solvents, and/or solidcarriers, optionally with the use of surfactants, i.e. emulsifiersand/or dispersants, and/or foam formers. The formulations are producedeither in suitable plants or else before or during application.

Suitable for use as auxiliaries are substances which are suitable forimparting to the composition itself and/or to preparations derivedtherefrom (for example spray liquors, seed dressings) particularproperties such as certain technical properties and/or also particularbiological properties. Typical auxiliaries include: extenders, solventsand carriers.

Suitable extenders are, for example, water, polar and nonpolar organicchemical liquids, for example from the classes of the aromatic andnon-aromatic hydrocarbons (such as paraffins, alkylbenzenes,alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, ifappropriate, may also be substituted, etherified and/or esterified), theketones (such as acetone, cyclohexanone), esters (including fats andoils) and (poly)ethers, the unsubstituted and substituted amines,amides, lactams (such as N-alkylpyrrolidones) and lactones, thesulphones and sulphoxides (such as dimethyl sulphoxide).

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Essentially, suitableliquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and also their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethyl sulphoxide, and also water.

Suitable solid carriers are:

for example ammonium salts and natural rock flours, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and synthetic rock flours, such as finely divided silica, aluminaand silicates; useful solid carriers for granules include: for example,crushed and fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, and also synthetic granules of inorganic andorganic flours, and granules of organic material such as paper, sawdust,coconut shells, maize cobs and tobacco stalks; useful emulsifiers and/orfoam-formers include: for example nonionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and also protein hydrolysates; suitabledispersants are nonionic and/or ionic substances, for example from theclasses of the alcohol-POE and/or -POP ethers, acid and/or POP POEesters, alkylaryl and/or POP POE ethers, fat and/or POP POE adducts,POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugaradducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl oraryl phosphates or the corresponding PO-ether adducts. Furthermore,suitable oligomers or polymers, for example those derived from vinylicmonomers, from acrylic acid, from EO and/or PO alone or in combinationwith, for example, (poly)alcohols or (poly)amines. It is also possibleto use lignin and its sulphonic acid derivatives, unmodified andmodified celluloses, aromatic and/or aliphatic sulphonic acids and alsotheir adducts with formaldehyde.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchas alizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

Other possible additives are perfumes, mineral or vegetable oils whichare optionally modified, waxes and nutrients (including tracenutrients), such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

Stabilizers, such as low-temperature stabilizers, preservatives,antioxidants, light stabilizers or other agents which improve chemicaland/or physical stability, may also be present.

The formulations generally comprise between 0.01 and 98% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances, herbicides,safeners, fertilizers or semiochemicals.

A mixture with other known active compounds, such as herbicides,fertilizers, growth regulators, safeners, semiochemicals, or else withagents for improving the plant properties, is also possible.

When used as insecticides, the inventive active compounds may also bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergists.Synergists are compounds which enhance the action of the activecompounds, without any need for the synergist added to be active itself.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with inhibitors which reduce degradation of the activecompound after use in the environment of the plant, on the surface ofparts of plants or in plant tissues.

The active compound content of the use forms prepared from thecommercially available formulations may vary within wide limits. Theactive compound concentration of the application forms may be from0.00000001 to 95% by weight of active compound, preferably between0.00001 and 1% by weight.

The compounds are employed in a customary manner appropriate for the useforms.

All plants and plant parts can be treated in accordance with theinvention. Plants are understood here to mean all plants and plantpopulations, such as desired and undesired wild plants or crop plants(including naturally occurring crop plants). Crop plants can thus beplants which can be obtained by conventional breeding and optimizationmethods or by biotechnological and genetic engineering methods orcombinations of these methods, including the transgenic plants andincluding the plant varieties which can or cannot be protected byvarietal property rights. Parts of plants are to be understood asmeaning all above-ground and below-ground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stems, trunks, flowers, fruit-bodies, fruits andseeds and also roots, tubers and rhizomes. The plant parts also includeharvested material and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, slips and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on, injection and, in thecase of propagation material, in particular in the case of seeds, alsoby applying one or more coats.

As already mentioned above, it is possible to treat all plants and theirparts in accordance with the invention. In a preferred embodiment, wildplant species and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The terms “parts” or“parts of plants” or “plant parts” have been explained above.

More preferably, plants of the plant cultivars which are eachcommercially available or in use are treated in accordance with theinvention. Plant cultivars are to be understood as meaning plants havingnew properties (“traits”) and which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. They may becultivars, biotypes and genotypes.

Depending on the plant species or plant cultivars, and the location andgrowth conditions (soils, climate, vegetation period, diet) thereof, theinventive treatment may also result in superadditive (“synergistic”)effects. For example, possibilities include reduced application ratesand/or broadening of the activity spectrum and/or an increase in theactivity of the compounds and compositions usable in accordance with theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to levels of water orsoil salinity, enhanced flowering performance, easier harvesting,accelerated ripening, higher yields, higher quality and/or highernutritional value of the harvested products, increased storage lifeand/or processibility of the harvested products, which exceed theeffects normally to be expected.

The transgenic plants or plant cultivars (those obtained by geneticengineering) which are to be treated with preference in accordance withthe invention include all plants which, through the geneticmodification, received genetic material which imparts particularadvantageous useful properties (“traits”) to these plants. Examples ofsuch properties are better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to levels of wateror soil salinity, enhanced flowering performance, easier harvesting,accelerated ripening, higher yields, higher quality and/or a highernutritional value of the harvested products, better storage life and/orprocessibility of the harvested products. Further and particularlyemphasized examples of such properties are an improved defence of theplants against animal and microbial pests, such as against insects,mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, sugar beet, tomatoes, peas and other types of vegetable,cotton, tobacco, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapes), with particular emphasis beinggiven to maize, soy beans, potatoes, cotton, tobacco and oilseed rape.Traits that are emphasized in particular are increased defence of theplants against insects, arachnids, nematodes and slugs and snails bytoxins formed in the plants, in particular those formed in the plants bythe genetic material from Bacillus thuringiensis (for example by thegenes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9cCry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelowreferred to as “Bt plants”). Traits that are also particularlyemphasized are the improved defence of plants against fungi, bacteriaand viruses by systemic acquired resistance (SAR), systemin,phytoalexins, elicitors and also resistance genes and correspondinglyexpressed proteins and toxins. Traits that are additionally particularlyemphasized are the increased tolerance of the plants to certain activeherbicidal compounds, for example imidazolinones, sulphonylureas,glyphosate or phosphinothricin (for example the “PAT” gene). The geneswhich impart the desired traits in question may also be present incombinations with one another in the transgenic plants. Examples of “Btplants” include maize varieties, cotton varieties, soya varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soy bean varieties which aresold under the trade names Roundup Ready® (tolerance against glyphosate,for example maize, cotton, soy beans), Liberty Link® (tolerance againstphosphinothricin, for example oilseed rape), IMI® (tolerance againstimidazolinones) and STS® (tolerance against sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to plant cultivars which have these genetic traitsor genetic traits which are still to be developed and will be developedand/or marketed in the future.

The plants stated can be treated particularly advantageously inaccordance with the invention with the compounds of the general formulaI or the active compound mixtures according to the invention. Thepreferred ranges stated above for the active compounds or mixtures alsoapply to the treatment of these plants. Particular emphasis is given tothe treatment of plants with the compounds or mixtures specificallymentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ecto- and endoparasites), suchas hard ticks, soft ticks, mange mites, leaf mites, flies (biting andlicking), parasitic fly larvae, lice, hair lice, feather lice and fleas.These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

from the order of the Heteropterida, for example Cimex spp., Triatomaspp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida, for example Blatta orientalis,Periplaneta americana, Blattella germanica and Supella spp.

From the subclass of the Acari (Acarina) and the orders of the Meta- andMesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp.,Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The inventive active compounds of the formula (I) are also suitable forcontrolling arthropods which attack agricultural livestock, for examplecattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits,chickens, turkeys, ducks, geese, honey-bees, other domestic animals suchas, for example, dogs, cats, caged birds, aquarium fish, andexperimental animals, for example hamsters, guinea pigs, rats and mice.The control of these arthropods is intended to reduce cases of death andreduced productivity (of meat, milk, wool, hides, eggs, honey etc.), andso more economic and easier animal husbandry is possible by use of theinventive active compounds.

The active compounds according to the invention are used in theveterinary sector and in animal husbandry in a known manner by enteraladministration in the form of, for example, tablets, capsules, potions,drenches, granules, pastes, boluses, the feed-through process andsuppositories, by parenteral administration, such as, for example, byinjection (intramuscular, subcutaneous, intravenous, intraperitoneal andthe like), implants, by nasal administration, by dermal use in the form,for example, of dipping or bathing, spraying, pouring on and spottingon, washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for livestock, poultry, domestic animals and the like, theactive compounds of the formula (I) can be used as formulations (forexample powders, emulsions, flowables) comprising the active compoundsin an amount of 1 to 80% by weight, either directly or after 100- to 10,000-fold dilution, or they may be used as a chemical bath.

It has also been found that the inventive compounds have stronginsecticidal action against insects which destroy industrial materials.

Preferred but nonlimiting examples include the following insects:

beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendronspec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec. Dinoderus minutus;

dermapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus, Urocerus augur;

termites, such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus;

bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are understood to meaninanimate materials, such as preferably plastics, adhesives, sizes,papers and cards, leather, wood, processed wood products and coatingcompositions.

The ready-to-use compositions may optionally also comprise otherinsecticides, and optionally one or more fungicides.

With respect to possible additional partners for mixing, reference ismade to the insecticides and fungicides mentioned above.

Moreover, the compounds according to the invention can be employed forprotecting objects which come into contact with saltwater or brackishwater, in particular hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Furthermore, the compounds according to the invention can be used aloneor in combinations with other active compounds as antifoulingcompositions.

The active compounds are also suitable for controlling animal pests inthe domestic sector, in the hygiene sector and in the protection ofstored products, especially insects, arachnids and mites, which arefound in enclosed spaces, for example homes, factory halls, offices,vehicle cabins and the like. They can be used to control these pestsalone or in combination with other active compounds and auxiliaries indomestic insecticide products. They are effective against sensitive andresistant species, and against all developmental stages. These pestsinclude:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellioscaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus,Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

From the order of the Coleoptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix,Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus, Triatoma infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active compounds, such as phosphoricacid esters, carbamates, pyrethroids, neonicotinoids, growth regulatorsor active compounds from other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orplastic, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

Description of the Preparation Processes and Intermediates

Anilines of the formula (II) are known (e.g. WO2007/043677,WO2008/126858, WO2008/126933) or can be prepared by known methods.

Synthesis of Carboxylic Acids of the Formula (IV-1) Example No. (IX)Synthesis of ethyl2-(bromomethyl)-4-(2-chlorophenyl)pyrimidine-5-carboxylate

820 mg (2.96 mmol) of ethyl4-(2-chlorophenyl)-2-methylpyrimidine-5-carboxylate and 633 mg (3.55mmol) of N-bromosuccinimide were dissolved in 18 ml of carbontetrachloride and, with stirring, heated to the boil. At boiling point,49 mg (0.29 mmol) of 2,2′-azobis-2-methylpropionitrile were added alittle at a time over a period of 5 hours, followed by refluxing for afurther hour. After cooling to room temperature, the reaction solutionwas filtered and the mother liquor was freed from the solvent underreduced pressure. The desired product was isolated by chromatographicpurification.

(logP: 3.32; MH⁺: 357; ¹H-NMR (400 MHz, DMSO, ppm): 1.00 (t, 3H), 4.12(q, 2H), 4.80 (s, 2H), 7.50 (m, 4H), 9.30 (s, 1H).

Example No. (X) Synthesis of ethyl4-(2-chlorophenyl)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]methylpyrimidine-5-carboxylate

345 mg (0.97 mmol) of ethyl2-(bromomethyl)-4-(2-chlorophenyl)pyrimidine-5-carboxylate were added toa solution of 200 mg (1.45 mmol) of trifluoromethyltetrazole in 10 ml ofacetonitrile. Then 174 mg (1.26 mmol) of potassium carbonate were addedto the reaction solution, and the mixture was stirred at 60° C. for 6hours. After cooling to room temperature, the reaction solution wasfiltered and the mother liquor was freed from the solvent under reducedpressure. 10 ml of water were added to the residue and the mixture wasextracted with ethyl acetate (3×20 ml). The combined organic phases weredried over sodium sulphate. The solvent was removed under reducedpressure and the residue was purified by chromatography. (logP: 3.56;MH⁺: 413; ¹H-NMR (400 MHz, DMSO, ppm): 0.99 (t, 3H), 4.13 (q, 2H), 6.62(s, 2H), 7.50 (m, 4H), 9.28 (s, 1H).

Example No. (IV-1) Synthesis of4-(2-chlorophenyl)-2-[5-(trifluoromethyl)-2H-tetrazol-2-yl]methylpyrimidine-5-carboxylicacid

1.74 g (4.21 mmol) of ethyl4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}pyrimidine-5-carboxylatewere dissolved in 12 ml of ethanol and 45% strength aqueous sodiumhydroxide solution (5.05 mmol) was added dropwise at 0° C. The reactionwas stirred for a further hour and warmed to RT. The ethanol was thenremoved under reduced pressure, and ice-water (10 ml) was added to theresidue. The aqueous phase was extracted with ethyl acetate. The organicphase was discarded. Then the aqueous phase was adjusted to a pH of 3using hydrochloric acid, and again extracted with ethyl acetate (3×20ml). The combined organic phases were dried over sodium sulphate. (logP:2.50; MH⁺: 385; ¹H-NMR (400 MHz, DMSO, ppm): 6.59 (s, 2H), 7.48 (m, 4H),9.27 (s, 1H).

Synthesis of carboxylic acids of the formula IV-2 Example No. XIISynthesis of methyl2-(bromomethyl)-4-(2-chlorophenyl)-1,3-thiazole-5-carboxylate

5.00 g (18.6 mmol) of methyl4-(2-chlorophenyl)-2-methyl-1,3-thiazole-5-carboxylate and 3.38 g (19.0mmol) of N-bromosuccinimide were dissolved in 100 ml of carbontetrachloride and, with stirring, heated to the boil. At boiling point,170 mg (1.00 mmol) of 2,2′-azobis-2-methylpropionitrile were added alittle at a time over a period of 5 hours, followed by refluxing for afurther hour. After cooling to room temperature, the reaction solutionwas filtered and the mother liquor was freed from the solvent underreduced pressure. The desired product was isolated by chromatographicpurification.

(logP: 4.12; MH⁺: 345; ¹H-NMR (400 MHz, DMSO, ppm): 3.70 (s, 3H), 5.76(s, 2H), 7.40-7.60 (m, 4H).

Example No. XIII Synthesis of methyl4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}-1,3-thiazole-5-carboxylate

5.00 g (14.4 mmol) of methyl2-(bromomethyl)-4-(2-chlorophenyl)-1,3-thiazole-5-carboxylate were addedto a solution of 10.00 g (18.7 mmol) of trifluoromethyltetrazole sodiumsalt in 100 ml of acetonitrile. Then 600 mg (4.32 mmol) of potassiumcarbonate were added to the reaction solution, and the mixture wasstirred at 60° C. for 6 hours. After cooling to room temperature, thereaction solution was filtered and the mother liquor was freed from thesolvent under reduced pressure. 10 ml of water were added to the residueand the mixture was extracted with ethyl acetate (3×20 ml). The combinedorganic phases were dried over sodium sulphate. The solvent was removedunder reduced pressure and the residue was purified by chromatography.(logP: 3.60; MH⁺: 404; ¹H-NMR (400 MHz, DMSO, ppm): 3.71 (s, 3H), 6.70(s, 2H), 7.40-7.60 (m, 4H).

Example No. X (IV-2) Synthesis of4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}-1,3-thiazole-5-carboxylicacid

3.60 g (8.91 mmol) of methyl4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}-1,3-thiazole-5-carboxylatewere dissolved in 18 ml of dioxane and 6 ml of water and 45% strengthaqueous sodium hydroxide solution (10.06 mmol) was added dropwise at 0°C. The reaction was stirred for a further hour and warmed to RT. Theethanol was then removed under reduced pressure, and ice-water (10 ml)was added to the residue. The aqueous phase was extracted with ethylacetate. The organic phase was discarded. Then the aqueous phase wasadjusted to a pH of 3 using hydrochloric acid, and again extracted withethyl acetate (3×20 ml). The combined organic phases were dried oversodium sulphate. (logP: 2.63; MH⁺: 390; ¹H-NMR (400 MHz, DMSO, ppm):6.65 (s, 2H), 7.36-7.55 (m, 4H).

Synthesis of carboxylic acids of the formula IV-3 Example No. XVSynthesis of methyl4-acetyl-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate

Under argon, 5.0 g (15.6 mmol) of methyl4-bromo-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate were dissolvedin THF, and 8.2 g (21.9 mmol) of (1-ethoxyvinyl)tributylstannane, 2.1 gof lithium chloride and 0.9 g (0.8 mmol) oftetrakis(triphenylphosphine)palladium were added at room temperature andthe mixture was stirred under reflux for 48 h. The solvent was thendistilled off, and the residue was taken up in 200 ml of THF and stirredin the presence of 12 ml of 2N hydrochloric acid at RT for a further 24h. Once more, the solvent was distilled off, and the residue wasdissolved in 120 ml of methyl tert-butyl ether and, at RT, stirredvigorously with 120 ml of saturated potassium fluoride solution for 1 h.The organic phase was separated off and concentrated. The desiredproduct was isolated by chromatographic purification.

(logP: 1.74; MH⁺: 279; ¹H-NMR (400 MHz, DMSO, ppm): 2.42 (s, 3H), 3.66(s, 3H), 7.63-7.66 (m, 1H), 8.12 (s, 1H), 8.21 (d, 1H), 8.54 (d, 1H).

Example No. XVI Synthesis of methyl4-(bromoacetyl)-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate

427 mg (1.48 mmol) of methyl4-acetyl-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate wereinitially charged in 12 ml of dioxane, and 284 mg (1.78 mmol) of brominewere added dropwise at RT. The mixture was then stirred under reflux for7 h. The solvent was distilled off under reduced pressure, giving an oilwhich was directly, without purification, reacted further.

(logP: 2.28; MH⁺: 358)

Example No. XVII Synthesis of methyl1-(3-chloropyridin-2-yl)-4-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]acetyl}-1H-pyrrole-2-carboxylate

890 mg (1.61 mmol) of 5-(trifluoromethyl)-2H-tetrazole and 297 mg (2.14mmol) of potassium carbonate were initially charged in 10 ml ofacetonitrile and heated at reflux for 15 min. 630 mg (1.07 mmol) ofmethyl4-(bromoacetyl)-1-(3-chloropyridin-2-yl)-1H-pyrrole-2-carboxylate,dissolved in 10 ml of acetonitrile, were added, and the reaction mixturewas stirred at 70° C. for 1 h. The solvent was distilled off, theresidue was taken up in water and the mixture was extracted twice withdichloromethane. The combined organic phases are washed with sodiumchloride solution, dried over sodium sulphate and concentrated. Thedesired product was isolated by chromatographic purification.

(logP: 2.97; MH⁺: 415; ¹H-NMR (400 MHz, DMSO, ppm): 3.69 (s, 3H), 6.65(s, 2H), 7.57 (s, 1H), 7.67-7.70 (m, 1H), 8.25 (d, 1H), 8.36 (s, 1H),8.57 (d, 1H).

Example No. IV-3 Synthesis of1-(3-chloropyridin-2-yl)-4-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]acetyl}-1H-pyrrole-2-carboxylicacid

130 mg (0.31 mmol) of methyl1-(3-chloropyridin-2-yl)-4-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]acetyl}-1H-pyrrole-2-carboxylatewere dissolved in 3 ml of ethanol, 19 mg (0.47 mmol) of 2N aqueoussodium hydroxide solution were added and the mixture was stirred at RTfor 4 h. The solvent was distilled off under reduced pressure, theresidue was taken up in water and the mixture was extracted once withmethyl tert-butyl ether. The aqueous phase was then acidified with 2Nhydrochloric acid and extracted three times with ethyl acetate. Thecombined organic phases were dried over sodium sulphate andconcentrated.

(logP: 2.24; MH⁺: 401)

Preparation Examples

The preparation processes described above can be used to give thecompounds of the formula (I)— for example the following compounds of theformula (I):

Synthesis of6-chloro-2-[4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}pyrimidin-5-yl]-8-methyl-4H-3,1-benzoxazin-4-one

At RT, 385 mg (1.30 mmol) of4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}pyrimidine-5-carboxylicacid was initially charged in 5 ml of acetonitrile, and 0.27 ml (2.33mmol) of lutidine was added. With stirring, the solution was then cooledto 0° C., 0.14 ml (1.78 mmol) of methanesulphonyl chloride, dissolved in2 ml of acetonitrile, was added dropwise and the mixture was stirred at0° C. for another 15 min. A little at a time, an acetonitrile suspension(3 ml) of 0.53 ml (4.54 mmol) of lutidine and 289 mg (1.56 mmol) of2-amino-5-chloro-3-methylbenzoic acid was then added to this reactionmixture, and stirring was continued for another 15 min. 0.14 ml (1.78mmol) of methanesulphonyl chloride, dissolved in 2 ml of acetonitrile,was then added dropwise. The reaction was stirred overnight, with thetemperature increasing to RT. The solvent was removed under reducedpressure. The residue was then poured into ice-water and mixed in anultrasonic bath. The residue was filtered off, again taken up in waterand sonicated once more. The residue is filtered off, washed with waterand dried under reduced pressure. 708 mg (88% of theory; content 86%) ofthe desired product were isolated. There was not further purification.

logP: 5.16; MH⁺: 534; ¹H-NMR (400 MHz, DMSO-d₆, δ, ppm): 1.96 (s, 3H),6.67 (s, 2H), 7.40-7.55 (m, 5H), 7.83 (m, 1H), 7.94 (m, 1H).

Synthesis ofN-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}pyrimidine-5-carboxamide

100 mg (0.18 mmol) of6-chloro-2-[4-(2-chlorophenyl)-2-{[5-(trifluoromethyl)-2H-tetrazol-2-yl]methyl}pyrimidin-5-yl]-8-methyl-4H-3,1-benzoxazin-4-onewere initially charged in 3 ml of THF, and 0.234 ml (0.46 mmol) of a 2molar methylamine/THF solution was added at RT. The reaction mixture wasthen stirred at 45° C. for 15 min. After cooling, the mixture wasconcentrated and purified chromatographically on silice gel usingcyclohexane/ethyl acetate. 48 mg (40% of theory; content 89%) of thedesired product were isolated.

logP: 3.13; MH⁺: 566; ¹H-NMR (400 MHz, DMSO-d₆, δ, ppm): 2.05 (s, 3H),2.69 (m, 3H), 6.60 (s, 2H), 7.35 (s, 1H), 7.40-7.55 (m, 4H), 8.32 (m,1H); 9.13 (s, 1H).

The examples below can be obtained in an analogous manner, some of thecompounds of the formula (I) being present as regioisomers. With respectto the NMR data, the table below states the chemical shifts and thecorresponding signal intensities; for example, for compound 1:

Signal 1:

10.272; 4.21; for 10.272 ppm (chemical shift), 4.21 (signal intensity);

Signal 2:

9.899; 0.35; for 9.899 ppm (chemical shift), 0.35 (signal intensity);

No. Structure log P MH+ NMR 1

3.98 614 (10.272;4.21),(9.899;0.35),(8.370;1.46),(8.360;1.45),(8.350;0.70),(7.642;0.44),(7.639;0.40),(7.637;0.39),(7.562;4.89),(7.542;3.41),(7.540;3.35),(7.528;2.10),(7.524;2.29),(7.510;3.13),(7.505;3.62),(7.499;4.18),(7.494;3.45),(7.479;1.98),(7.474;1.78),(7.460;3.04),(7.455;2.54),(7.440;1.89),(7.435;1.71),(7.407;2.18),(7.404;2.16),(7.388;2.82),(7.385;2.65),(7.369;1.06),(7.366;1.01),(7.301;0.39),(6.706;12.44),(6.644;0.87),(6.598;0.53),(6.468;0.58),(4.040;0.62),(4.022;0.60),(3.380;0.46),(3.358;0.75),(3.321;2.64),(3.288;1167.97),(3.252;1.33),(3.228;0.60),(3.202;0.40),(2.890;0.35),(2.732;0.45),(2.695;0.57),(2.672;1.90),(2.668;2.41),(2.654;10.21),(2.642;10.01),(2.605;0.96),(2.593;0.96),(2.538;8.56),(2.521;7.60),(2.508;108.05),(2.503;210.37),(2.499;278.91),(2.494;197.59),(2.490;92.86),(2.407;0.65),(2.330;1.35),(2.326;1.84),(2.321;1.30),(2.316;0.73),(2.210;0.77),(2.158;1.30),(2.114;15.00),(2.095;1.07),(2.067;2.47),(2.049;1.34),(1.986;2.65),(1.962;1.18),(1.293;0.71),(1.237;0.87),(1.193;0.77),(1.175;1.48),(1.157;0.87),(0.008;1.54),(−0.000;32.01),(−0.009;1.13) 2

4.34 598 (10.088;0.36),(8.190;1.14),(8.177;1.17),(7.554;1.44),(7.552;1.53),(7.541;1.84),(7.539;1.81),(7.512;124),(7.509;1.42),(7.499;1.65),(7.497;1.80),(7.471;0.93),(7.468;1.02),(7.458;1.54),(7.456;1.40),(7.445;1.14),(7.442;1.03),(7.435;1.75),(7.434;1.76),(7.431;2.03),(7.430;1.87),(7.401;1.25),(7.399;124),(7.396;0.35),(7.389;1.88),(7.386;1.84),(7.376;0.82),(7.374;0.82),(7.323;1.98),(7.319;1.92),(6.705;7.83),(6.619;0.95),(6.476;0.44),(3.887;0.52),(3.876;0.77),(3.863;0.75),(3.852;0.51),(3.344;455.59),(3.325;0.59),(3.320;0.58),(3.318;0.49),(2.884;1.07),(2.618;0.59),(2.615;0.85),(2.612;0.60),(2.542;4.85),(2.524;1.47),(2.521;1.89),(2.518;1.74),(2.509;44.47),(2.506;100.07),(2.503;137.84),(2.500;99.26),(2.497;44.89),(2.405;0.38),(2.390;0.64),(2.387;0.92),(2.384;0.66),(2.216;0.58),(2.153;0.45),(2.122;9.53),(2.102;0.72),(2.097;0.77),(2.077;1.50),(2.053;0.73),(1.918;0.43),(1.397;12.10),(1.292;0.37),(1.113;1.01),(1.102;1.00),(1.087;1.54),(1.076;1.58),(1.061;0.98),(1.051;0.98),(0.977;1.01),(0.966;13.50),(0.955;12.69),(0.005;0.81) 3

3.45 601 (9.988;2.73),(9.866;0.46),(7.879;1.50),(7.715;0.51),(7.710;0.49),(7.617;0.56),(7.576;3.08),(7.546;4.65),(7.541;3.66),(7.522;2.60),(7.517;2.94),(7.502;4.98),(7.498;5.10),(7.490;3.56),(7.454;1.56),(7.449;1.89),(7.436;3.17),(7.431;2.65),(7.417;3.88),(7.412;3.31), (7.398;1.92),(7.378;0.82),(7.301;0.48),(7.026;0.62),(7.005;0.54),(6.871;0.57),(6.718;0.65),(6.675;10.68),(6.628;0.48),(6.263;0.49),(5.742;8.23),(3.602;0.48),(3.567;0.54),(3.470;0.45),(3.453;0.55),(3.422;0.64),(3.404;0.74),(3.395;0.95),(3.288;1896.54),(3.265;32.89),(3.228;0.78),(2.907;0.68),(2.695;0.52),(2.672;3.08),(2.668;4.03),(2.663;3.01),(2.639;0.49),(2.627;0.56),(2.615;0.68),(2.597;0.77),(2.566;1.24).(2.538;6.31),(2.521;16.64),(2.508;226.17),(2.503;439.87),(2.499;583.78),(2.494;412.79),(2.490;193.00), (2.405;5.02),(2.335;1.37),(2.330;2.69),(2.326;3.66),(2.321;2.55),(2.204;1.79),(2.183;1.05),(2.102;15.00),(2.067;1.03),(2.048;1.11),(1.997;0.71),(1.986;0.55),(1.907;0.63),(1.357;7.10),(1.246;2.61),(1.238;1.07),(1.175;0.49),(1.091;0.56),(0.891;0.84),(0.008;4.77),(−0.000;96.17),(−0.008;3.25) 4

3.12 562 (9.569;3.38),(9.561;2.92),(8.797;2.30),(8.554;2.92),(8.366;2.93),(8.284;1.17),(8.273;1.21),(8.237;2.95),(8.208;1.46),(8.196;1.51),(8.085;1.28),(8.039;1.59),(8.035;1.63),(7.979;3.04),(7.958;1.93),(7.843;2.68),(7.823;3.90),(7.695;1.85),7.672;1.40),(7.543;1.58),(7.523;4.00),(7.513;1.73),(7.505;1.79),(7.498;2.15),(7.491;2.74),(7.478;1.28),(7.471;1.44),(7.459;1.80),(7.454;2.63),(7.441;7.14),(7.439;6.11),(7.423;4.57),(7.415;5.00),(7.408;4.25),(7.398;3.15),(7.380;3.15),(7.374;2.13),(7.361;3.29),(7.356;3.02),(7.343;1.92),(7.335;3.37),(7.329;3.08),(7.321;4.15),(7.315;3.33),(5.654;6.11),(5.311;3.46),(5.282;339),(4.040;3.33),(4.022;3.43),(3.290;1061.61),(2.684;2.12),(2.673;3.55),(2.668;3.02),(2.661;9.01),(2.652;14.18),(2.640;10.86),(2.625;1.79),(2.613;1.67),(2.538;8.76),(2.521;7.47),(2.508;106.42),(2.504;208.63),(2.499;278.27),(2.494;196.94),(2.490;92.43),(2.330;1.36), (2.326;1.80),(2.321;1.34),(2.214;2.59),(2.159;11.81),(2.129;14.91),(2.109;2.80),(2.067;1.20),(2.049;1.49),(1.986;15.00),(1.193;4.21),(1.175;8.33),(1.157;4.16),(0.008;1.13),(−0.000;25.35) 5

4.48 642 (10.061;2.78),(8.151;1.25),(8.131;1.26),(7.548;3.69),(7.530;2.33),(7.527;2.37),(7.509;1.31),(7.504;1.54),(7.489;1.91),(7.485;2.10),(7.474;1.21),(7.470;1.16),(7.455;2.14),(7.451;1.81),(7.441;2.79),(7.436;3.59),(7.431;1.58),(7.403;1.61),(7.399;1.54),(7.384;1.99),(7.380;1.87),(7.365;0.78),(7.362;0.72),(6.688;8.65),(6.462;0.64),(4.039;0.58),(3.899;0.66),(3.882;1.00),(3.866;0.93),(3.847;0.64),(3.398;0.96),(3.366;1.42),(3.353;2.29),(3.293;3174.69),(3.271;32.58),(3.238;2.02),(3.230;1.25),(3.226;1.17),(3.174;0.60),(2.677;1.57),(2.673;3.05),(2.668;4.09),(2.664;3.12),(2.584;0.58),(2.538;6.14),(2.522;16.14),(2.508;233.09),(2.504;458.49),(2.499;613.11),(2.495;434.14),(2.490;204.73),(2.335;1.49),(2.331;3.00),(2.326;3.94), (2.321;2.81),(2.317;139),(2.151;0.57),(2.119;10.71),(2.095;1.00),(2.084;2.33),(2.067;0.88),(2.048;1.09),(1.986;2.32),(1.399;3.01),(1.237;1.16),(1.193;0.75),(1.175;1.74),(1.168;1.76),(1.158;0.98),(1.092;0.93),(1.075;1.09),(1.071;1.31),(1.054;0.99),(0.988;1.84),(0.977;15.00),(0.960;14.64),(0.891;0.85),(0.008;3.19),(−0.000;71.66),(−0.008;2.49) 6

3.25 545 (10.589;1.10),(8.533;0.87),(7.865;2.92),(7.830;3.67),(7.825;3.16),(7.804;0.43),(7.665;1.95),(7.661;2.04),(7.646;2.49),(7.642;2.62),(7.620;1.91),(7.618;2.00),(7.600;3.55),(7.597;3.41),(7.585;0.48),(7.575;1.73),(7.571;1.82),(7.557;2.55),(7.553;2.36),(7.537;1.44),(7.532;1.23),(7.478;1.93),(7.475;1.94),(7.459;2.66),(7.456;2.62),(7.440;1.22),(7.437;1.17),(7.430;0.31),(6.625;11.62),(6.532;0.77),(6.358;0.84),(3.387;0.35),(3.376;0.37),(3.357;0.42),(3.290;663.56),(3.271;2.03),(3.256;0.62),(3.249;0.46),(2.858;4.27),(2.743;1.40),(2.731;1.83),(2.721;9.58),(2.709;9.44),(2.695;1.23),(2.683;1.00),(2.673;0.91),(2.668;1.08),(2.664;0.81),(2.591;0.42),(2.582;2.29),(2.570;2.19),(2.554;0.48),(2.538;4.69),(2.522;4.06),(2.508;55.84),(2.504;108.12),(2.499;142.78),(2.495;100.13),(2.490;46.20),(2.331;0.70),(2.326;0.90),(2.322;0.63),(2.275;0.59),(2.222;15.00),(2.209;1.70),(2.132;0.64),(2.099;1.22),(2.067;0.63),(2.049;0.69),(1.986;1.01),(1.293;0.36),(1.238;0.50),(1.193;0.36),(1.175;0.62),(1.158;0.33),(0.008;0.70),(−0.000;14.39),(−0.008;0.42) 7

3.95 587 (7.824;0.53),(7.725;0.63),(7.658;0.49),(7.655;0.54),(7.639;0.61),(7.635;0.63),(7.612;0.39),(7.595;0.82),(7.592;0.77),(7.576;0.38),(7.573;0.38).(7.558;0.52),(7.554;0.46),(7.478;0.42),(7.474;0.40),(7.459;0.56),(7.456;0.55),(6.624;2.30),(3.289;324.31),(2.914;0.37),(2.673;0.35),(2.668;0.47),(2.664;0.35),(2.538;2.32),(2.521;1.98),(2.508;27.37),(2.503;53.02),(2.499;70.11),(2.494;49.15),(2.490;22.66),(2.330;0.34),(2.326;0.45),(2.321;0.32),(2.229;2.87),(2.091;0.56),(2.067;0.32),(2.049;0.36),(1.399;4.23),(1.368;2.51),(1.265;0.37),(1.258;1.27),(1.211;0.94),(1.198;15.00),(−0.000;4.70) 8

4.75 612 (9.857;0.97),(7.722;0.97),(7.552;0.51),(7.550;0.55),(7.533;0.80),(7.530;0.77),(7.523;0.31),(7.502;0.49),(7.498;0.64),(7.484;0.72),(7.479,0.89),(7.472;0.50),(7.458;0.75),(7.453;0.59),(7.438;0.53),(7.433;0.40),(7.407;0.56),(7.403;0.59),(7.396;0.84),(7.388;1.18),(7.385;0.73),(7.250;0.90),(7.244;0.78),(6.675;2.99),(6.643;0.48),(3.292;524.17),(3.269;7.71),(2.673;0.62),(2.668;0.81),(2.664;0.60),(2.659;0.31),(2.538;1.33),(2.521;3.70),(2.508;45.90),(2.504;88.96),(2.499;117.97),(2.495;83.54),(2.490;39.28),(2.330;0.53),(2.326;0.71),(2.321;0.50),(2.208;0.31),(2.157;0.59),(2.121;3.64),(2.067;0.41),(1.903;0.54),(1.399;1.91),(1.301;0.51),(1.285;2.65),(1.258;0.59),(1.237;0.42),(1.136;15.00), (−0.000;0.48) 9

3.5 568 (10.358;0.35),(8.002;1.93),(7.722;0.42),(7.718;0.42),(7.656;1.89),(7.654;2.03),(7.644;2.35),(7.641;2.36),(7.636;0.33),(7.632;0.57),(7.628;0.63),(7.617;5.45),(7.616;5.90),(7.613;4.99),(7.604;3.22),(7.602;3.02),(7.595;0.32),(7.592;043),(7.575;3.20),(7.571;2.86),(7.569;2.08),(7.566;1.69),(7.562;0.36),(7.556;2.16),(7.554;2.04),(7.547;0.72),(7.543;1.80),(7.540;1.36),(7.528;0.35),(7.517;0.38),(7.513;0.43),(7.477;1.61),(7.475;1.58),(7.464;2.37),(7.463;2.32),(7.452;1.13),(7.450;1.11),(7.308;0.37),(7.305;0.38),(7.117;1.48),(6.613;10.31),(6.585;0.70),(6.343;0.44),(6.298;0.59),(3.400;0.35),(3.388;0.94),(3.376;1.22),(3.349:385.18),(3.321;0.42),(2.911;0.43),(2.618;0.64),(2.615;0.89),(2.612;0.64),(2.524;1.71),(2.521;2.11),(2.518;2.06),(2.510;47.18),(2.507;102.21),(2.503;141.07),(2.500;102.64),(2.497;47.08),(2.394;0.32), (2.391;0.66),(2.388;0.93),(2.385;0.66),(2.382;0.32),(2.297;10.39),(2.215;0.95),(2.201;2.17),(2.169;13.50),(2.152;0.81),(2.102;2.09),(2.087;0.31),(2.077;0.84),(1.993;0.92),(1.990;0.48),(1.102;0.79),(1.091;1.60) 10

3.63 570 (9.987;0.71),(8.380;0.66),(8.372;0.66),(7.572;0.41),(7.569;0.44),(7.541;0.50),(7.519;1.14),(7.506;1.35),(7.501;0.63),(7.492;0.93),(7.489;0.94),(7.480;1.07),(7.477;1.11),(7.459;1.34),(7.455;1.43),(7.447;0.66),(7.444;0.69),(7.434;1.01),(7.431 ;0.94),(7.421;0.74),(7.418;0.66),(7.409;0.87),(7.396;0.93),(7.381;0.51),(7.377;0.37),(7.358;1.43),(7.355;1.37),(6.701;4.07),(3.346;323.35),(3.326;0.50),(3.323;0.53),(2.676;1.48),(2.671;3.58),(2.664;3.41),(2.621;0.33),(2.618;0.61),(2.615;0.84),(2.612;0.60),(2.609;0.30),(2.524;1.37),(2.521;1.75),(2.518;1.70),(2.509;40.48),(2.506;88.93),(2.503;122.93),(2.500;90.02),(2.497;41.16),(2.393;0.31),(2.390;0.63),(2.387;0.85),(2.384;0.73),(2.381;0.59),(2.372;6.77),(2.297;13.50),(2.212;1.02),(2.117;0.86),(2.107;6.31),(2.077;1.04),(1.910;0.28),(−0.000;8.27) 11

4.28 642 (9.797;1.43),(8.189;0.59),(8.170;0.66),(7.697;0.37),(7.650;0.43),(7.610:0.62),(7.594;0.50),(7.556;1.43),(7.518;0.95),(7.515;1.01),(7.498;1.41),(7.496;1.47),(7.465;0.98),(7.456;0.94),(7.450;0.99),(7.441;1.99),(7.437;2.62),(7.418;0.96),(7.412;0.88),(7.407;0.95),(7.389;0.96),(7.368;0.47),(6.684;4.10),(3.940;0.43),(3.923;0.64),(3.906;0.68),(3.890;0.43),(3.394;0.35),(3.292;371.20),(3.170;0.62),(2.695;0.33),(2.672;0.95),(2.668;1.27),(2.664;0.98),(2.538;5.69),(2.521;5.40),(2.508;72.92),(2.503;142.17),(2.499;188.71),(2.494;133.99),(2.490;63.11),(2.330;0.85), (2.326;1.21),(2.321;0.89),(2.294;9.45),(2.212;0.68),(2.100;0.97),(2.072;5.68),(2.067;4.65),(2.048;0.95),(1.818;0.69),(1.293;0.46),(1.237;0.36),(1.179;15.00),(1.163;14.71),(1.099;0.33),(1.091;0.54),(1.069;9.67),(1.052;9.55),(1.040;1.42),(1.018;0.42),(−0.000;20.17),(−0.009;0.74) 12

3.73 614 (9.929;0.37),(8.322;1.01),(7.674;0.34),(7.612;0.38),(7.602;0.34),(7.573;1.91),(7.515;1.79),(7.495;3.21),(7.473;3.66),(7.451;1.53),(7.446;1.56),(7.432;2.28),(7.427;2.02),(7.408;2.27),(7.390;1.48),(7.368;0.89),(7.297;0.43),(7.284;0.35),(7.263;0.43),(7.233;0.30),(6.682;5.88),(6.490;0.33),(3.445;0.33),(3.432;0.32),(3.382;0.49),(3.368;0.72),(3.288;1183.09),(3.248;1.31),(3.230;0.49),(3.202;0.33),(2.890;1.13),(2.732;1.07),(2.695;1.02),(2.672;6.92),(2.663;6.08),(2.622;0.63),(2.616;0.64),(2.600;0.61),(2.538;9.97),(2.521;8.94),(2.508;122.15),(2.503;238.04),(2.499;316.72),(2.494;224.10),(2.490;105.54),(2.406;0.53), (2.376;15.00),(2.330;1.52),(2.326;2.08),(2.321;1.40),(2.292;11.43),(2.209;0.86),(2.098;7.02),(2.067;6.38),(2.048;1.99),(1.821;0.70),(1.356;0.48),(1.292;0.77),(1.236;0.59),(1.229;0.52),(1.159;0.49),(1.147;0.43),(0.008;1.83),(−0.000;37.58), (−0.009;1.27) 13

3.34 556 (9.989;3.10),(7.871;1.72),(7.542;0.35),(7.522;2.40),(7.518;2.80),(7.503;5.54),(7.499;5.63),(7.449;3.85),(7.444;3.82),(7.436;3.93),(7.431;3.53),(7.424;5.38),(7.418;6.72),(7.412;3.80),(7.399;2.05),(7.382;0.74),(6.677;11.03),(6.629;0.30),(4.507;0.31),(4.057;1.13),(4.040;3.42),(4.022;3.40),(4.004;1.19),(3.353;0.46),(3.347;0.48),(3.286;568.48),(3.244;0.50),(2.673;0.88),(2.668;1.20),(2.663;0.92),(2.538;1.97),(2.521;5.52),(2.508;71.43),(2.503;137.28),(2.499;181.52),(2.494;128.45),(2.490;60.77),(2.405;1.41), (2.330;0.87),(2.326;1.12),(2.321;0.82),(2.107;14.82),(2.067;1.33),(2.048;0.39),(1.986;15.00),(1.237;0.78),(1.193;4.22),(1.175;8.33),(1.157;4.16),(1.143;1.78),(0.008;1.53),(−0.000;30.10), (−0.008;1.13) 14

3.19 561 (10.260;5.13),(10.169;1.17),(8.436;1.44),(8.399;0.59),(7.995;0.98),(7.894;0.95),(7.831;2.94),(7.800;1.12),(7.796;1.09),(7.765;4.29),(7.533;0.33),(7.514;2.84),(7.495;4.54),(7.473;1.89),(7.451;1.53),(7.446;1.74),(7.432;3.22),(7.427;2.70),(7.413;2.68),(7.408;3.27),(7.387;2.12),(7.369;0.76),(6.958;1.00),(6.689;14.82),(6.634;0.84),(3.515;0.31),(3.403;0.47),(3.337;1.34),(3.286;902.63),(3.248;0.53),(3.239;0.32),(2.857;5.72),(2.747;0.33),(2.697;3.87),(2.685;13.99),(2.673;12.41),(2.634;0.96),(2.622;0.96),(2.582;3.28),(2.569;3.29),(2.538;3.29),(2.521;8.00),(2.508;104.26),(2.503;200.60),(2.499;264.66),(2.494;187.38),(2.490;87.91),(2.330;1.18),(2.326;1.58),(2.321;1.09), (2.277;4.17),(2.182;0.31),(2.143;15.00),(2.132;5.42),(2.115;0.67),(2.067;1.18),(2.049;0.49),(1.986;0.78),(1.259;0.36),(1.238;0.84),(1.175;0.47),(1.143;0.77),(−0.000;31.49),(−0.008;1.13) 15

3.69 573 (10.359;2.98),(10.099;0.48),(8.281;1.30),(8.262;1.35),(8.008;0.45),(7.885;0.45),(7.857;2.56),(7.784;2.64),(7.780;2.54),(7.765;0.46),(7.761;0.46),(7.657;1.41),(7.653;1.46),(7.638;1.76),(7.634;1.83),(7.613;1.15),(7.611;1.28),(7.593;2.56),(7.590;2.50),(7.574;1.37),(7.570;1.33),(7.556;1.79),(7.552;1.62),(7.535;0.94),(7.531;0.80),(7.504;0.44),(7.473;1.33),(7.469;1.29),(7.454;1.79),(7.451;1.74),(7.436;0.85),(7.432;0.73),(7.004;0.46),(6.624;8.55),(6.364;0.57),(3.958;0.71),(3.942;1.07),(3.923;1.10),(3.907;0.74),(3.376;0.35),(3.364;0.40),(3.347;0.48),(3.287;471.80),(3.248;0.38),(3.244;0.33),(2.878;1.70),(2.673;0.69),(2.668;0.87),(2.663;0.67),(2.576;0.51),(2.538;1.47),(2.508;50.27),(2.503;97.02),(2.499;128.26),(2.494;90.84),(2.490;42.88),(2.330;0.59),(2.326;0.80), (2.321;0.58),(2.286;1.87),(2.230;10.81),(2.214;1.02),(2.128;1.78),(2.067;0.60),(1.986;0.35),(1.237;0.36),(1.120;1.69),(1.103;1.70),(1.082;2.79),(1.074;0.72),(1.066;2.78),(1.050;2.44),(1.043;15.00),(1.034;2.95),(1.026;14.66),(−0.000;12.20), (−0.008;0.42)16

3.65 554 (10.219;4.04),(10.143;0.33),(8.400;1.47),(8.389;1.48),(7.654;1.85),(7.650;2.01),(7.635;2.48),(7.631;2.54),(7.614;1.92),(7.611;1.97),(7.594;3.66),(7.591;3.64),(7.569;2.04),(7.565;2.04),(7.550;2.82),(7.546;2.63),(7.530;1.60),(7.526;1.33),(7.470;4.60),(7.464;3.64),(7.455;3.00),(7.451;2.67),(7.436;1.22),(7.433;1.16),(7.407;3.65),(7.401;3.05),(6.616;11.43),(6.573;0.65),(6.532;0.37),(6.352;0.69),(3.414;0.34),(3.389;0.44),(3.344;0.84),(3.341;0.83),(3.287;612.72),(2.726;0.40),(2.696;10.02),(2.685;10.00),(2.673;1.55),(2.668;1.39),(2.663;1.04),(2.620;0.78),(2.608;0.73),(2.572;0.72),(2.538;2.21),(2.521;5.51),(2.508;68.34),(2.503;130.43),(2.499;171.28),(2.494;120.33),(2.490;56.02),(2.330;0.81),(2.326;1.06),(2.321;0.75), (2.226;0.87),(2.215;0.49),(2.177;15.00),(2.164;1.47),(2.110;0.38),(2.067;0.72),(2.029;0.84),(1.986;0.30),(1.238;0.49),(−0.000;18.38), (−0.008;0.61) 17

3.73 589 (10.154;3.08),(10.099;0.53),(8.293;1.21),(8.274;1.17),(8.003;0.40),(7.889;0.42),(7.824;2.25),(7.766;0.53),(7.761;0.59),(7.747;2.58),(7.743;2.34),(7.544;0.31),(7.518;1.29),(7.514;1.39),(7.498;2.27),(7.495;2.65),(7.489;1.20),(7.475;1.44),(7.470;1.60),(7.455;0.90),(7.450;1.04),(7.437;2.00),(7.432;1.51),(7.418;1.53),(7.410;1.69),(7.405;1.45),(7.391;1.44),(7.387;1.32),(7.372;0.47),(7.276;0.33),(7.003;0.45),(6.692;8.48),(6.633;0.54),(3.947;0.67),(3.930;1.00),(3.912;1.00),(3.895;0.69),(3.880;0.32),(3.359;0.47),(3.349;0.54),(3.340;0.68),(3.334;0.76),(3.288;465.72),(3.265;0.90),(3.250;0.42),(2.878;1.61),(2.677;0.37),(2.673;0.66),(2.668;0.84),(2.664;0.67),(2.538;1.40),(2.521;3.82),(2.508;48.03),(2.503;92.27),(2.499;121.60),(2.494;85.90),(2.490;40.32),(2.330;0.55), (2.326;0.77),(2.321;0.55),(2.286;1.81),(2.120;10.16),(2.067;0.57),(2.045;0.81),(1.399;0.57),(1.237;0.37),(1.220;0.59),(1.198;0.57),(1.181;0.58),(1.145;0.67),(1.120;1.71),(1.103;1.93),(1.085;14.93),(1.069;15.00),(1.057;1.61),(1.002;0.80),(0.986;0.80),(0.008;0.52),(−0.000;9.87),(−0.008;0.35) 18

4.46 596 (9.792;1.00),(7.806;0.38),(7.680;0.95),(7.646;0.64),(7.643;0.52),(7.627;0.79),(7.624;0.68),(7.612;0.54),(7.609;0.53),(7.592;0.94),(7.589;0.94),(7.573;0.50),(7.569;0.50),(7.555;0.77),(7.535;0.54),(7.531;0.43),(7.477;0.54),(7.473;0.51),(7.458;0.65),(7.455;0.62),(7.439;0.41),(7.432;0.81),(7.427;0.84),(7.272;0.86),(7.267;0.81),(6.656;1.08),(6.618;2.85),(3.351;0.38),(3.339;0.53),(3.326;0.78),(3.287;405.26),(3.240;0.38),(2.673;0.57),(2.668;0.82),(2.664;0.56),(2.538;1.20),(2.521;3.46),(2.508;45.09),(2.503;86.46),(2.499;113.87),(2.494;80.41),(2.490;38.03),(2.335;0.34),(2.330;0.58),(2.326;0.79),(2.321;0.57),(2.221;0.35),(2.207;0.37),(2.183;3.52),(2.162;0.32),(2.084;1.27),(2.067;0.37),(1.976;0.31),(1.399;7.60),(1.323;0.87),(1.281;1.38),(1.258;0.82),(1.237;0.65),(1.182;1.48),(1.169;15.00),(0.008;0.63),(−0.000;12.07),(−0.008;0.46) 19

4.11 582 (9.980;2.99),(8.130;1.34),(8.111;1.33),(7.644;1.40),(7.640;1.47),(7.625;1.77),(7.621;1.89),(7.606;1.25),(7.588;2.67),(7.585;2.67),(7.568;1.46),(7.564;1.58),(7.550;1.91),(7.546;1.94),(7.530;1.18),(7.525;0.97),(7.470;1.48),(7.466;1.50),(7.458;2.34),(7.451;3.95),(7.432;0.88),(7.429;0.87),(7.343;2.45),(7.337;2.39),(6.613;8.21),(6.569;0.48),(6.358;0.54),(3.936;0.65),(3.920;0.97),(3.902;0.99),(3.884;0.62),(3.359;0.33),(3.337;0.78),(3.286;821.35),(3.264;3.24),(3.243;1.02),(3.232;0.64),(3.217;0.47),(3.209;0.45),(3.181;0.33),(2.878;0.52),(2.672;1.20),(2.668;1.46),(2.663;1.13),(2.566;0.50),(2.538;2.18),(2.508;88.43),(2.503;172.72),(2.499;230.42),(2.494;164.79),(2.490;78.91),(2.421;0.34),(2.404;0.40),(2.334;0.69), (2.330;1.20),(2.326;1.60),(2.321;1.18),(2.218;0.73),(2.182;10.82),(2.165;1.05),(2.115;0.59),(2.067;0.80),(2.048;0.35),(2.002;0.64),(1.986;0.77),(1.237;0.58),(1.175;0.42),(1.143;1.24),(1.130;0.61),(1.119;0.60),(1.113;0.62),(1.103;0.52),(1.064;1.06),(1.047;0.99),(1.019;1.95),(1.010;15.00),(0.993;14.69),(0.008;1.51),(−0.000;31.10),(−0.008;1.13) 20

3.45 540 (10.319;3.92),(10.272:0.43),(7.945;1.77),(7.658;2.01),(7.654;2.21),(7.639;2.68),(7.635;2.80),(7.613;1.88),(7.610;2.08),(7.593;3.63),(7.590;3.72),(7.569;2.87),(7.565;3.49),(7.551;3.28),(7.547;2.87),(7.531;1.73),(7.527;1.50),(7.474;4.37),(7.468;4.27),(7.454;6.22),(7.448;2.86),(7.440;1.60),(7.436;1.46),(7.416;0.31),(6.600;11.06),(6.573;0.43),(6.524;0.63),(6.336;0.84),(4.058;0.44),(4.040;1.23),(4.022;1.24),(4.004;0.38),(3.376;0.35),(3.288;811.89),(3.263;2.05),(3.236;0.45),(3.226;0.38),(2.908;2.63),(2.673;1.00),(2.668;1.33),(2.664;1.00),(2.562;0.76),(2.538;2.22),(2.521;5.77),(2.508;78.08),(2.503;151.32),(2.499;200.22),(2.494;141.72),(2.490;66.55),(2.331;0.99), (2.326;1.33),(2.321;0.95),(2.220;0.57),(2.211;0.94),(2.174;15.00),(2.157;1.59),(2.109;0.87),(2.067;0.43),(2.049;0.34),(2.005;0.46),(1.986;5.36),(1.399;0.40),(1.260;0.34),(1.237;0.70),(1.193;1.55),(1.175;3.07),(1.157;1.52),(−0.000;8.81) 21

3.72 598 (10.220;4.05),(10.145;0.36),(8.404;1,53),(8.393;1.42),(7.667;0.62),(7.653;1.92),(7.649;2.05),(7.634;2.56),(7.630;2.57),(7.614;2.16),(7.11;2.36),(7.595;6.70),(7.591;4.84),(7.569;2.02),(7.565;2.02),(7.550;2.78),(7.546;2.51),(7.530;4.78),(7.526;3.86),(7.473;1.99),(7.470;1.88),(7.455;2.69),(7.452;2.48),(7.436;1.17),(7.433;1.10),(6.614;11.44),(6.570;0.45),(6.532;0.52),(6.350;0.72),(5.742;1.36),(3.457;0.34),(3.444;0.40),(3.433;0.39),(3.422;0.51),(3.406;0.47),(3.372;0.78),(3.361;0.98),(3.350;1.26),(3.291;1150.47),(3.263;1.94),(3.245;0.46),(3.240;0.43),(2.694;10.26),(2.683;10.38),(2.668;1.93),(2.664;1.38),(2.618;0.63),(2.607;0.62),(2.588;0.41),(2.571;0.77),(2.538;2.70),(2.521;6.72),(2.508;88.67),(2.504;171.37),(2.499;226.67),(2.495;160.36),(2.490;75.44),(2.330;1.14), (2.326;1.38),(2.322;0.96),(2.222;0.58),(2.210;0.65),(2.173;15.00),(2.161;1.60),(2.105;0.80),(2.067;1.58),(2.049;0.34),(2.024;0.59),(1.399;0.33),(1.237;0.69),(1.143;0.50),(0.891;0.31), (−0.000;5.52) 22

4.52 640 (9.788;0.98),(7.689;1.04),(7.672;0.31),(7.669;0.32),(7.646;0.59),(7.642;0.54),(7.627;0.81),(7.623;0.71),(7.609;0.56),(7.593;0.96),(7.589;0.99),(7.573;0.60),(7.569;0.78),(7.564;0.88),(7.560;0.94),(7.555;0.95),(7.551;0.77),(7.535;0.52),(7.477;0.48),(7.473;0.49),(7.458;0.68),(7.455;0.70),(7.439;0.30),(7.436;0.30),(7.393;0.85),(7.387;0.82),(6.655;0.69),(6.616;2.82),(3.290;390.54),(2.914;2.43),(2.673;0.47),(2.668;0.65),(2.664;0.52),(2.538;1.09),(2.521;2.74),(2.508;36.60),(2.504;70.94),(2.499;94.11),(2.494;66.79),(2.490;31.47),(2.330;0.49),(2.326;0.60),(2.321 ;0.46),(2.316;0.46),(2.217;0.31),(2.180;3.53),(2.159;0.31 ),(2.079;0.85),(2.067;0.60),(1.655;1.38),(1.399;9.88),(1.336;0.32),(1.323;1.12),(1.284;1.36),(1.258;7.15),(1.247;0.43),(1.237;0.50),(1.181;1.56),(1.169;15.00),(0.008;0.43),(−0.000;9.05),(−0.008;0.32) 23

4.21 626 (9.984;2.89),(8.141;134),(8.122;1.34),(7.644;1.34),(7.640;1.49),(7.624;1.79),(7.621;1.87),(7.605;1.39),(7.588;4.43),(7.585;4.98),(7.568;1.48),(7.564;1.51),(7.550;1.92),(7.546;1.78),(7.530;1.04),(7.525;0.90),(7.466;3.66),(7.460;2.64),(7.451;2.14),(7.448;1.83),(7.432;0.97),(7.429;0.92),(6.613;8.29),(6.567;0.48),(6.514;0.39),(6.357;0.52),(3.952;0.31),(3.935;0.67),(3.919;1.05),(3.902;0.97),(3.884;0.64),(3.355;0.35),(3.286;656.24),(3.240;0.57),(3.230;0.45),(3.223;0.42),(3.216;0.38),(3.210;0.37),(2.877;1.93),(2.677;0.58),(2.672;1.04),(2.668;1.29),(2.663;0.92),(2.566;0.40),(2.538;2.12),(2.521;5.52),(2.508;76.68),(2.503;148.33),(2.499;196.43),(2.494;139.48),(2.490;66.19),(2.421;0.35),(2.335;0.66),(2.330;1.00), (2.326;1.31),(2.321;0.91),(2.215;0.71),(2.179;10.77),(2.162;1.07),(2.115;0.67),(2.067;1.64),(2.049;0.40),(1.997;0.58),(1.440;0.31),(1.423;0.30),(1.399;2.60),(1.238;0.54),(1.143;1.66),(1.130;0.79),(1.119;1.96),(1.114;0.96),(1.103;1,87),(1.067;1.04),(1.050;0.94),(1.020;2.05),(1.011;15.00),(0.994;14.70),(0.008;1.51),(−0.000;30.14),(−0.009;1.12) 24

3.46 560 (10.654;3.64),(10.169;0.62),(8.497;1.42),(8.485;1.47),(8.410;0.31),(8.398;0.33),(7.996;0.58),(7.992;0.56),(7.893;0.56),(7.826;3.47),(7.796;4.36),(7.570;2.00),(7.567;2.07),(7.550;3.17),(7.547;3.10),(7.539;1.98),(7.535;2.12),(7.520;2.60),(7.516;2.82),(7.486;1.35),(7.482;1.43),(7.467;2.60),(7.463;2.12),(7.448;1.70),(7.443;1.40),(7.425;0.41),(7.413;1.96),(7.410;1.96),(7.394;2.57),(7.391;2.46),(7.376;1.02),(7373;0.91),(6.960;0.61),(6.718;12.51),(6.477;0.51),(4.058;0.38),(4.040;1.03),(4.022;1.11),(4.004;0.39),(3.440;0.35),(3.426;0.30),(3.400;0.37),(3.375;0.63),(3.346;0.97),(3.328;1.75),(3.289;892.22),(3.254;0.94),(2.857;3.05),(2.742;1.05),(2.731;1.07),(2.697;2.06),(2.680;10.17),(2.668;11.07),(2.650;0.58),(2.582;1.83),(2.569;1.85),(2.538;2.40),(2.521;6.13),(2.508;82.52),(2.504;159.84),(2.499;211.72),(2.494;149.90),(2.490;70.75),(2.330;0.97),(2326;127),(2.321;0.98), (2.277;2.42),(2.244;0.32),(2.159;15.00),(2.141;1.14),(2.132;2.52),(2.098;1.40),(2.067;0.38),(2.049;0.35),(1.986;4.67),(1.238;0.45),(1.193;1.32),(1.175;2.65),(1.157;1.28),(−0.000;7.74) 25

3.7 589 (10.154;3.08),(10.099;0.53),(8.293;1.21),(8.274;1.17),(8.003;0.40),(7.889;0.42),(7.824;2.25),(7.766;0.53),(7.761;0.59),(7.747;2.58),(7.743;2.34),(7.544;0.31),(7.518;1.29),(7.514;1.39),(7.498;2.27),(7.495;2.65),(7.489;1.20),(7.475;1.44),(7.470;1.60),(7.455;0.90),(7.450;1.04),(7.437;2.00),(7.432;1.51),(7.418;1.53),(7.410;1.69),(7.405;1.45),(7.391;1.44),(7.387;1.32),(7.372;0.47),(7.276;0.33),(7.003;0.45),(6.692;8.48),(6.633;0.54),(3.947;0.67),(3.930;1.00),(3.912;1.00),(3.895;0.69),(3.880;0.32),(3.359;0.47),(3.349;0.54),(3.340;0.68),(3.334;0.76),(3.288;465.72),(3.265;0.90),(3.250;0.42),(2.878;1.61),(2.677;0.37),(2.673;0.66),(2.668;0.84),(2.664;0.67),(2.538;1.40),(2.521;3.82),(2.508;48.03),(2.503;92.27),(2.499;121.60),(2.494;85.90),(2.490;40.32),(2.330;0.55), (2.326;0.77),(2.321;0.55),(2.286;1.81),(2.120;10.16),(2.067;0.57),(2.045;0.81),(1.399;0.57),(1.237;0.37),(1.220;0.59),(1.198;0.57),(1.181;0.58),(1.145;0.67),(1.120;1.71),(1.103;1.93),(1.085;14.93),(1.069;15.00),(1.057;1.61),(1.002;0.80),(0.986;0.80),(0.008;0.52),(−0.000;9.87),(−0.008;0.35) 26

4.69 656 (9.644;0.89),(7.750;0.80),(7.531;1.06),(7.527;1.04),(7.511;0.69),(7.508;0.67),(7.488;0.33),(7.483;0.38),(7.470;0.53),(7.465;0.78),(7.447;0.66),(7.442;0.44),(7.428;0.45),(7.423;0.33),(7.415;0.50),(7.411;0.51),(7.392;1.21),(7.386;0.80),(6.690;2.52),(3.323;0.30),(3.285;179.92),(2.668;0.39),(2.538;0.61),(2.521;1.67),(2.508;22.60),(2.503;43.85),(2.499;58.18),(2.494;41.34),(2.490;19.66),(2.326;0.37), (2.048;3.46),(1.399;3.25),(1.257;15.00),(1.147;0.46),(−0.000;4.74) 27

4.59 612 (9.643;0.80),(7.736;0.80),(7.528;0.47),(7.509;0.72),(7.485;0.40),(7.465;0.81),(7.448;0.60),(7.428;0.40),(7.412;0.55),(7.396; 1.19),(7.272;0.79),(6.690;2.34),(3.370;0.42),(3.292;755.22),(2.673;0.72),(2.668;0.98),(2.664;0.71),(2.538;1.56),(2.521;3.96),(2.508;56.59),(2.504;109.81),(2.499;145.54),(2.494;103.80),(2.490;49.44),(2.330;0.70),(2.326;0.94), (2.321;0.68),(2.067;1.65),(2.051;4.07),(1.256;15.00),(1.237;0.91),(−0.000;3.07) 28

4.29 603 (10.188;1.04),(7.891;0.95),(7.795;0.79),(7.792;0.84),(7.698;0.90),(7.694;0.83),(7.558;0.45),(7.555;0.48),(7.538;0.75),(7.535;0.75),(7.520;0.45),(7.516;0.50),(7.501;0.61),(7.497;0.70),(7.483;0.35),(7.479;0.35),(7.465;0.64),(7.460;0,49),(7.445;0.41),(7.440;0.31),(7.411;0.48),(7.408;0.48),(7.393;0.64),(7.390;0.60),(6.689;3.03),(3.288;303.81),(2.914;3.10),(2.672;0.41),(2.668;0.54),(2.663;0.40),(2.538;0.93),(2.521;2.32),(2.508;30.06),(2.503;57.99),(2.499;76.67),(2.494;54.35),(2.490;25.58),(2.330;0.36), (2.326;0.48),(2.321;0.33),(2.166;3.66),(2.067;0.34),(1.399;2.40),(1.258;9.18),(1.169;15.00),(1.107;0.45),(−0.000;4.49) 29

4.83 656 (9.855;0.97),(7.735;0.93),(7.553;0.46),(7.550;0.48),(7.530;1.35),(7.523;0.82),(7.503;0.43),(7.498;0.46),(7.484;0.60),(7.480;0.75),(7.472;0.36),(7.458;0.66),(7.453;0.46),(7.438;0.41),(7.406;0.50),(7.403;0.46),(7.388;0.64),(7.384;0.60),(7.369;1.03),(7.365;0.88),(6.674;2.91),(3.289;260.58),(3.266;1.22),(2.890;0.32),(2.668;0.42),(2.538;0.70),(2.521;1.86),(2.508;23.16),(2.503;44.03),(2.499;57.70),(2.494;40.55),(2.490;18.90),(2.326;0.35),(2.118;3.61),(2.067;0.45),(1.137;15.00),(−0.000;1.72) 30

4.07 603 (9.995;1.09),(7.892;0.90),(7.798;0.76),(7.795;0.79),(7.712;0.87),(7.708;0.81),(7.530;0.41),(7.527;0.44),(7.510;0.65),(7.507;0.69),(7.496;0.40),(7.492;0.40),(7.478;0.58),(7.473;0.67),(7.461;0.31),(7.447;0.64),(7.442;0.46),(7.428;0.44),(7.422;0.36),(7.418;0.53),(7.414,0.51),(7.399;0.53),(7.396;0.48),(6.697;3.01),(3.289;191.50),(2.668;0.35),(2.538;0.60),(2.521;1.48),(2.508;19.64),(2.503;37.90),(2.499;50.12),(2.494;35.46),(2.490;16.65),(2.326;0.31), (2.095;3.50),(2.084;0.88),(1.274;15.00),(1.107;0.34),(0.008;0.31),(−0.000;6.22) 31

2.78 2.83 553 (9.907;3.99),(9.902;4.46),(8.798;2.03),(8.594;5.64),(8.434;1.02),(8.423;1.09),(8.372;3.44),(8.251;7.12),(8.064;0.99),(8.040;1.43),(7.981;2.58),(7.960;1.65),(7.845;2.19),(7.824;4.36),(7.818;2.90),(7.808;2.98),(7.756;2.74),(7.752;2.64),(7.741;3.23),(7.737;2.81),(7.697;1.53),(7.680;1.20),(7.544;1.00),(7.528;2.76),(7.517;1.38),(7.511;1.32),(7.502;1.64),(7.496;1.94),(7.481;0.88),(7.476;1.43),(7.469;1.17),(7.460;1.76),(7.455;4.07),(7.448;4.23),(7.437;2.52),(7.429;2.65),(7.425;1.53),(7.412;1.93),(7.406;2.19),(7.397;0.90),(7.384;2.02),(7.379;1.35),(7.366;3.02),(7.361;2.20),(7.348;1.49),(7.344;1.13),(5.661;5.52),(5.360;0.85),(5.321;2.82),(5.291;2.72),(5.252;0.89),(3.394;0.79),(3.331;2.89),(3.289;1820.16),(3.241;1.54),(3.077;1.03),(2.678;8.35),(2.668;15.00),(2.657;9.02),(2.610;0.60),(2.576;0.87),(2.538;4.94),(2.521;12.93),(2.508;167.56),(2.503;322.86),(2.499;426.89),(2.494;301.29),(2.490;141.85),(2.330;2.07),(2.326;2.69), (2321;1.95),(2.201;10.77),(2.175;12.79),(2.067;1.01),(2.049;0.60),(1.237;1.07),(1.107;3.59),(0.008;2.21),(−0.000;42.38),(−0.008;1.53) 32

4.15 598 (9.805;2.15),(8.191;0.89),(8.172;0.92),(7.521;0.98),(7.517;1.20),(7.501;1.72),(7.498;1.88),(7.490;0.78),(7.486;0.81),(7.468;1.16),(7.457;0.80),(7.452;0.89),(7.438;1.94),(7.433;2.46),(7.426;1.73),(7.419;1.48),(7.413;1.12),(7.409;1.15),(7.405;1.14),(7.391;1.07),(7.387;1.02),(7.369;0.39),(7.320;2.29),(7.314;2.09),(6.688;6.51),(3.942;0.55),(3.925;0.83),(3.907;0.83),(3.890;0.55),(3.307;1395.40),(3.286;2.93),(3.284;2.99),(3.261;0.57),(3.251;0.48),(2.678;0.40),(2.674;0.92),(2.669;1.32),(2.664;0.97),(2.660;0.39),(2.539;1.82),(2.523;2.96),(2.518;4.47),(2.509;69.12),(2.505;138.11),(2.500;189.23),(2.496;128.68),(2.491;60.03),(2.336;0.43),(2.331;0.97),(2.327;1.33), (2.322;0.94),(2.318;0.45),(2.076;8.52),(2.049;0.37),(1.236;0.48),(1.068;15.00),(1.051;14.92),(−0.000;5.23) 33

2.75 572 (10.327;4.85),(8.523;3.11),(8.519;3.40),(8.511;3.41),(8.508;3.34),(8.373;4.68),(8.369;4.70),(8.358;0.92),(8.346;1.84),(8.335;1.85),(8.160;2.69),(8.156;2.75),(8.139;2.90),(8.136;2.84),(7.839;3.72),(7.749;4.03),(7.745;3.90),(7.699;4.39),(7.695;4.43),(7.608;2.71),(7.596;2.64),(7.588;2.60),(7.576;2.74),(6.615;13.56),(4.095;0.52),(4.039;0.54),(4.021;0.61),(3.341;2.34),(3.304;2412.98),(3.281;8.17),(3.263;1.33),(3.241;0.61),(3.232;0.67),(2.858;7.44),(2.716;1.07),(2.704;1.18),(2.684;11.00),(2.673;12.46),(2.664;3.07),(2.660;1.45),(2.581;3.88),(2.568;3.91),(2.539;5.04),(2.522;8.01),(2.518;11.83),(2.509;157.46),(2.504;311.75),(2.500;425.12),(2.495;294.21),(2.491;140.21), (2.336;1.02),(2.331;2.05),(2.327;2.89),(2.322;2.02),(2.273;1.38),(2.209;16.00),(2.069;2.95),(2.049;0.66),(1.987;2.63),(1.258;0.50),(1.237;2.61),(1.193;0.97),(1.175;1.70),(1.157;1.00),(1.127;0.73),(1.113;1.96),(1.109;1.50),(1.098;1.95),(1.091;0.79),(0.008;2.33),(−0.000;72.01),(−0.008;2.37) 34

3.91 593 (10.259;0.31),(10.240;3.40),(9.133;6.05),(8.266;1.50),(8.246;1.50),(7.517;1.05),(7.500;2.72),(7.489;1.52),(7.483;1.51),(7.473;1.54),(7.467;2.01),(7.461;1.17),(7.455;1.62),(7.448;1.85),(7.441;3.23),(7.432;2.84),(7.427;3.73),(7.420;3.53),(7.397;0.59),(7.393;0.54),(7.325;2.90),(7.319;2.75),(6.605;8.47),(6.398;0.58),(3.973;0.65),(3.956;1.00),(3.939;1.00),(3.921;0.65),(3.306;374.18),(3.210;0.42).(2.674;0.48),(2.669;0.61),(2.664;0.48),(2.539;1.46),(2.504;69.08),(2.500;86.17),(2.496;62.29),(2.425;0.39),(2.327;0.69),(2.322;0.54),(2.069;0.93),(2.031;11.83),(2.012;0.73),(1.987;0.32),(1.398;1.91),(1.237;0.35),(1.087;14.95),(1.071;15.00),(1.035;0.45),(1.018;0.38),(−0.000;6.72) 35

3.01 551 (10.344;0.30),(10.334;0.33),(10.305;4.35),(9.179;0.35),(9.142;7.79),(7.840;2.15),(7.526;1.57),(7.513;1.55),(7.507;2.75),(7.502;2.79),(7.489;1.75),(7.483;2.35),(7.474;3.04),(7.467;4.83),(7.462;6.42),(7.457;5.47),(7.451;5.07),(7.445;4.32),(7.439;4.51),(7.434;5.23),(7.414;0.86),(7.393;4.11),(7.387;3.31),(6.603;10.93),(6.394;0.53),(3.530;0.31),(3.471;0.50),(3.308;991.99),(3.238;1.02),(3.192;0.41),(3.128;0.30),(2.731;0.31),(2.694;0.30),(2.673;1.07),(2.669;1.34),(2.609;0.47),(2.592;0.55),(2.539;8.38),(2.508;80.27),(2.504;141.87),(2.500;179.30),(2.496;126.41),(2.412;0.35),(2.331;0.96),(2.326;1.23),(2.322;0.94), (2.097;0.40),(2.084;3.55),(2.069;3.08),(2.058;15.00),(1.987;0.50),(1.907;0.30),(1.398;10.46),(1.292;0.35),(1.235;0.65),(1.107;0.30),(0.890;0.43),(−0.000;2.02) 36

3.31 565 (10.313;0.31),(10.306;0.34),( 10.279;4.50),(9.170;0.54),(9.134;7.99),(8.332;1.74),(8321;1.67),(7.522;1.48),(7.504;3.64),(7.489;1.82),(7.483;2.00),(7.473;2.16),(7.467;2.72),(7.461;1.62),(7.454;2.16),(7.448;2.71),(7.441;5.03),(7.436;5.73),(7.431;6.60),(7.414;2.28),(7.411;2.17),(7.395;0.83),(7.391;0.70),(7.350;4.07),(7.344;3.61),(6.604;11.12),(6.394;0.59),(4.039;0.38),(4.021;0.37),(3.303;442.85),(2.691;9.96),(2.680;9.72),(2.669;1.46),(2.664;1.01),(2.539;2.09),(2.508;49.81),(2.504;87.03),(2.500;108.65),(2.495;75.66),(2.335;0.40),(2.331;0.64),(2.326;0.82),(2.322;0.62),(2.069;0.80),(2.040;15.00),(1.987;1.62),(1.398;2.22),(1.237;0.68),(1.224;030),(1.192;0.52),(1.175;0.89),(1.157;0.47),(0,890;0.34),(−0.000;7.17),(−0.008;0.37) 37

3.5 584 (10.506;2.95),(9.149;4.91),(8.326;1.31),(8.307;1.29),(7.826;2.56),(7.762;0.34),(7.739;2.88),(7.735;2.72),(7.517;0.93),(7.498;2.65),(7.490;1.56),(7.483;1.42),(7.474;1.46),(7.468;2.16),(7.457;1.24),(7.448;2.44),(7.444;2.81),(7.438;2,84),(7.434;2.11),(7.422;1.28),(7.418;1.24),(7.403;0.46),(7.399;0.40),(6.616;7.82),(6.407;0.33),(4.039;0.38),(4.021;0.40),(3.960;0.61),(3.943;0.97),(3.925;0.95),(3.909;0.61),(3.301;252.17),(2.673;0.51),(2.669;0.67),(2.664;0.51),(2.539;1.64),(2.508;40.24),(2.504;70.87),(2.500;89.15),(2.495;62.26),(2.331;0.53),(2.326;0.68),(2.322;0.50).(2.286;1.24),(2.126;1.28),(2.089;9.46),(2.069;0.71),(1.987;1.72),(1.398;8.09),(1.237;0.70),(1.193;0.55),(1.175;1.01),(1.157;0.57),(1.088;15.00),(1.081;4.76),(1.072;14.94),(1.065;3.62),(−0.000;5.45) 38

2.93 556 (10.544;4.62),(10.173;0.58),(9.188;0.31),(9.149;7.22),(8.418;2.11),(8.407;1.91),(7.997;0.57),(7.900;0.62),(7.837;4.14),(7.802;0.63),(7.756;4.51),(7.522;1.71),(7.518;1.63),(7.504;4.47),(7.491;2.20),(7.485;2.14),(7.475;2.63),(7.469;3.94),(7.464;2.44),(7.451;5.83),(7.438;2.94),(7.435;2.67),(7.423;2.36),(7.403;0.59),(6.965;0.58),(6.614;11.96),(6.403;0.50),(4.039;0.96),(4.021;0.97),(4.004;0.36),(3.536;0.30),(3.517;0.36),(3.502;0.41),(3.483;0.43),(3.311;938.39),(3.288;14.63),(3.230;0.62),(3.206;0.35),(2.693;10.41),(2.682;10.28),(2.670;1.90),(2.639;0.33),(2.539;3.24),(2.505;117.82),(2.500;147.75),(2.496;104.00),(2.403;0.34),(2.327;1.07),(2.323;0.77),(2.277;2.49),(2.131;2.72),(2.099;15.00),(2.069;1.63),(2.050;0.44),(1.987;3.86),(1.908;0.78),(1.237;0.55),(1.193;1.05),(1.175;2.08),(1.157;1.11),(0.890;0.32),(−0.000;5.25) 39

3.85 598 (10.470;1.10),(9.121;1.91),(7.999;0.93),(7.795;0.93),(7.717;0.99),(7.713;0.94),(7.525;0.38),(7.506;0.96),(7.492;0.38),(7.484;0.41),(7.479;0.41),(7.470;0.61),(7.451;0.65),(7.438;1.64),(7.424;0.51),(6.618;2.84),(3.302;127.15),(3.278;2.95),(2.539;0.66),(2.504;28.83),(2.500;35.92),(2.496;25.60),(2.065;3.49),(1.288;15.00),(1.276;1.38),(1.263;0.93),(−0.000;2.18) 40

2.69 542 (10.590;2.35),(9.193;0.39),(9.183;0.38),(9.156;15.00),(8.041;1.12),(8.005;0.41),(7.988;0.50),(7.926;1.50),(7.898;1.33),(7.878;0.85),(7.853;1.74),(7.806;6.03),(7.609;0.36),(7.590;0.48),(7.567;1.01),(7.550;1.09),(7.519;4.86),(7.499;6.00),(7.461;7.24),(7.446;7.00),(7.425;2.84),(7.024;0.61),(6.605;12.82),(6.396;0.63),(4.057;1.11),(4.039;3.02),(4.021;3.03),(4.004;1.09),(3.457;0.49),(3.430;0.64),(3.424;0.74),(3.305;1129.01),(3.181;0.50),(3.145;0.42),(2.891;0.38),(2.731;0.39),(2.695;0.40),(2.674;1.34),(2.669;1.74),(2.664;1.32),(2.622;0.41),(2.615;0.47),(2.594;0.63),(2.579;0.81),(2.539;11.18),(2.508;110.51),(2.504;193.28),(2.500;241.77),(2.496;168.56),(2.402;0.64), (2.394;0.53),(2.384;0.45),(2.331;1.47),(2.326;1.86),(2.267;2.76),(2.245;0.48),(2.214;0.38),(2.199;0.38),(2.188;0.41),(2.175;0.51),(2.170;0.50),(2.130;5.98),(2.109;13.59),(2.069;2.56),(2.050;1.25),(2.039;0.62),(2.004;0.47),(1.987;13.11),(1.955;0.45),(1.905;1.06),(1.398;0.98),(1.299;0.38),(1.293;0.52),(1.260;0.42),(1.238;1.01),(1.193;3.67),(1.175;7.14),(1.157;3.56),(0.890;0.63),(−0.000;5.60) 41

4.33 607 (10.253;0.36),(9.108;0.47),(7.980;0.34),(7.513;0.34),(7.433;0.67),(7.401;0.53),(7.286;0.41),(6.623;0.73),(3.380;1.74),(3.352;3952.17),(3.328;126.58),(2.621;1.58),(2.618;3.42),(2.615;4.70), (2.612;3.36),(2.609;1.54),(2.524;9.15),(2.521;11.75),(2.518;11.99),(2.509;248.89),(2.506;532.96),(2.503;720.27),(2.500;512.66),(2.497;229.26),(2.393;1.41),(2.390;3.23), (2.387;4.47),(2.384;3.12),(2.381;1.32),(2.205;0.31),(2.076;13.50),(2.008;1.15),(1.286;3.52),(1.234;0.82),(0.005;1.05),(0.000;31.06), (−0.006;0.87) 42

3.31 543 (10.13;3.41),(8.42;0.54),(8.41;1.46),(8.40;1.46),(8.40;0.53),(7.82;2.98),(7.82;3.16),(7.73;3.52),(7.73;3.35),(7.54;2.25),(7.53;1.70),(7.53;1,52),(7.52;1.91),(7.52;2.77),(7.44;1.51),(7.44;1.21),(7.44;1.37),(7.43;1.57),(7.43;1.69),(7.43;3.79),(7.42;1.28),(7.41;3.46),(7.41;4.82),(7.40;6.03),(7.40;3.59),(7.39;1.96),(7.38;0.54),(7.35;3.51),(7.35;3.70),(7.24;3.77),(7.23;3.71),(6.05;10.18),(3.57;0.47),(3.36;612.67),(3.34;4.50),(2.66;11.78),(2.65;11.98),(2.62;0.52),(2.62;0.74),(2.61;0.53),(2.54;0.40),(2.52;1.46),(2.52;1.83),(2.52;1.76),(2.51;38.01),(2.51;83.37), 2.50;114.48),(2.50;81.76),(2.50;37.64),(2.39;0.50),(2.39;0.75),(2.38;0.51),(2.17;16.00),(2.08;0.81),(1.99;0.60),(1.17;0.33) 43

3.75 552 (9.78;4.26),(8.21;1.64),(8.20;1.57),(7.53;1.70),(7.52;1.98),(7.52;1.38),(7.51;1.96),(7.51;1.85),(7.51;1.83),(7.50;0.54),(7.43;1.03),(7.42;3.24),(7.41;10.53),(7.40;7.79),(7.39;6.50),(7.38;1.64),(7.37;0.37),(7.31;7.67),(7.31;6.69),(7.19;3.97),(7.18;3.66),(6.04;9.99),(3.49;0.32),(3.48;0.33),(3.46;0.39),(3.44;0.50),(3.31;872.39),(3.29;10.05),(2.83;0.57),(2.74;0.62),(2.67;1.44),(2.65;10.20),(2.64;10.15),(2.58;0.86),(2.54;1.82),(2.51;59.15).(2.50;105.95),(2.50;135.20),(2.50;95.17),(2.49;47.00),(2.43;0.35),(2.33;0.73),(2.33;0.96),(2.32;0.71),(2.16;0.39),(2.13;16.00),(2.11;0.83),(2.07;0.50), (0.00;7.85) 44

4.09 602 (9.81;4.38),(8.23;1.61),(8.22;1.58),(7.53;1.61),(7.53;1.61),(7.52;1.19),(7.52;1.84),(7.51;1.97),(7.50;0.33),(7.44;0.85),(7.42;1.87),(7.42;1.98),(7.41;7.52),(7.41;7.57),(7.41;7.38),(7.41;6.82),(7.40;5.39),(7.39;1.10),(7.38;1.74),(7.32;4.26),(7.32;4.55),(7.31;3.99),(7.31;3.34),(7.19;3.85),(7.18;3.59),(6.07;9.67),(3.32;335.26),(3.30;3.75),(3.08;1.03),(2.67;0.76),(2.67;0.60),(2.65;10.04),(2.64;10.11),(2.54;0.34),(2.52;1.23),(2.51;86.86),(2.50;113.84),(2.50;78.39),(2.33;0.69),(2.13;16.00),(2.07;0.87),(1.24;0.34),(1.11;2.98),(0.00;6.08)

Analytical Methods:

The logP values reported in the table above and in the PreparationExamples were determined in accordance with EEC Directive 79/831 AnnexV.A8 by HPLC (High Performance Liquid Chromatography) on reversed-phasecolumns (C 18), with the following methods:

The LC-MS determination in the acidic range is carried out at pH 2.7using the mobile phases 0.1% aqueous formic acid and acetonitrile(contains 0.1% formic acid), linear gradient from 10% acetonitrile to95% acetonitrile

Calibration was carried out using unbranched alkan-2-ones (having from 3to 16 carbon atoms) with known logP values (the logP values weredetermined by the retention times using linear interpolation between twosuccessive alkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

The MH+ signals were determined using an Agilent MSD system with ESI andpositive or negative ionisation.

The NMR spectra were determined using a Bruker Avance 400 fitted with aflow probe head (volume 60 μl). The solvent used was d6-DMSO, withtetramethylsilane (0.00 ppm) being employed as reference. The examplesin the table above were recorded in d6-DMSO as solvent. The measuringtemperature was 303K.

In individual cases, the samples were measured using a Bruker Avance II600 or III 600.

USE EXAMPLES Example 1 Spodoptera frugiperda Test SPODFR Spray Treatment

Solvents: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvents andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration. Discs of maize leaves (Zea mays) aresprayed with an active compound preparation of the desired concentrationand, after drying, populated with caterpillars of the armyworm(Spodoptera frugiperda). After 7 days, the effect in % is determined100% means that all caterpillars have been killed; 0% means that none ofthe caterpillars have been killed.

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an effect of 83%:11

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of 100%:

13, 14, 25, 26, 27, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43,44

Example 2 Phaedon Test PHAECO Spray Treatment

Solvents: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvents andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration. Discs of Chinese cabbage (Brassicapekinensis) are sprayed with an active compound preparation of thedesired concentration and, after drying, populated with larvae of themustard beetle (Phaedon cochleariae).

After 7 days, the activity in % is determined. 100% means that allbeetle larvae have been killed; 0% means that none of the beetle larvaehave been killed.

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of83%:11, 12

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of 100%:

10, 13, 25, 26, 27, 30, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44

Example 3 Tetranychus Test, OP-Resistant TETRUR Spray Treatment

Solvents: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvents andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration. Discs of bean leaves (Phaseolusvulgaris) which are infested by all stages of the greenhouse red spidermite (Tetranychus urticae) are sprayed with an active compoundpreparation of the desired concentration.

After 6 days, the activity in % is determined. 100% means that all ofthe spider mites have been killed; 0% means that none of the spidermites have been killed.

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of 80%:8

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of 100%:3

Example 4 Myzus Test MYZUPE Spray Treatment

Solvents: 78 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvents andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Discs of Chinese cabbage (Brassica pekinensis) infested by all stages ofthe green peach aphid (Myzus persicae) are sprayed with an activecompound preparation of the desired concentration.

After 6 days, the effect in % is determined. 100% means that all of theaphids have been killed; 0% means that none of the aphids have beenkilled.

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of 80%:42

In this test, for example, the following compounds of the PreparationExamples show, at an application rate of 100 g/ha, an activity of100%:43

Example 5 Boophilus microplus Test BOOPMI Injection

Solvent: dimethyl sulphoxide

To produce a suitable preparation of active compound, 10 mg of activecompound are mixed with 0.5 ml of solvent and the concentrate is dilutedwith solvent to the desired concentration. The active compound solutionis injected into the abdomen (Boophilus microplus), and the animals aretransferred into dishes and stored in a climate-controlled room. Theactivity is assessed by position of fertile eggs.

After 7 days, the effect in % is determined. 100% means that none of theticks has laid any fertile eggs.

In this test, for example, the following compounds of the PreparationExamples show an activity of 100% at an application rate of 20μg/animal: 34, 37, 38, 39, 40, 41.

In this test, for example, the following compounds of the PreparationExamples show an activity of 98% at an application rate of 20 μg/animal:35

Example 6 Musca domestica Test MUSCDO

Solvent: dimethyl sulphoxide

To produce a suitable preparation of active compound, 10 mg of activecompound are mixed with 0.5 ml of dimethyl sulphoxide and theconcentrate is diluted with water to the desired concentration. Vesselscontaining a sponge treated with the active compound preparation of thedesired concentration are populated with adult Musca domestica.

After 2 days, the kill in % is determined. 100% means that all of theflies have been killed; 0% means that none of the flies have beenkilled.

In this test, for example, the following compounds of the PreparationExamples show an efficacy of 100% at an application rate of 100 ppm: 37

Example 7 Lucilia cuprina Test LUCICU

Solvent: dimethyl sulphoxide

To produce a suitable preparation of active compound, 10 mg of activecompound are mixed with 0.5 ml of dimethyl sulphoxide and theconcentrate is diluted with water to the desired concentration. Vesselscontaining horse meat treated with the active compound preparation ofthe desired concentration are populated with about 20 Lucilia cuprinalarvae.

After 2 days, the kill in % is determined. 100% means that all of thelarvae have been killed; 0% means that none of the larvae have beenkilled.

In this test, for example, the following compounds of the PreparationExamples show an efficacy of 100% at an application rate of 100 ppm: 3,34, 35, 37, 38, 39, 40, 41.

The invention claimed is:
 1. An anthranilic acid derivative of formula (I)

in which R¹ represents hydrogen, R² represents hydrogen, R³ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyano-n-propyl, 2-cyano-n-propyl, 3-cyano-n-propyl, 1-cyanoisopropyl,2-cyanoisopropyl, phenyl or pyridyl, R⁴ represents hydrogen, methyl, trifluoromethyl, cyano, fluorine, chlorine, bromine, iodine or trifluoromethoxy or two adjacent radicals R⁴ represent —(CH₂)₄—or —(CH═CH—)₂— n represents 0 to 3, R⁵ represents methyl, fluorine, chlorine, bromine or iodine, Q_(X) represents thiazole, oxazole, pyrrole, imidazole, triazole, pyrimidine, or phenyl, which is monosubstituted by the group R⁷

A represents —CH₂—, —CH(CH₃), C(CH₃)₂, —CH₂CH₂—, —CH(CN)—, —CH₂ O —or —C(═O)—CH₂—, Q_(Y) represents an optionally mono- or polysubstituted 5- or 6-membered heteroaromatic ring selected from the group consisting of Q-36 to Q-40, Q43, Q-58 to Q-59,Q62, Q63, an aromatic 9-membered fused heterobicyclic ring system Q-54 to Q-56 or a 5-membered heterocyclic ring Q-60 to Q-61 where the substituents independently of one another may be selected from the group consisting of C₁-C₃-alkyl, C₁-C₃-haloalkyl, C₁-C₂-alkoxy, halogen, cyano, hydroxyl, nitro and C₁-C₂-haloalkoxy or where the substituents independently of one another may be selected from the group consisting of phenyl and a 5- or 6-membered heteroaromatic ring, where phenyl or the ring may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₆-cycloalkyl, C₁-C₆-haloalkyl, C₂-C₆-haloalkenyl, C₂-C₆-haloalkynyl, C₃-C₆-halocycloalkyl, halogen, CN, NO₂, OH, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, R⁹ independently represents fluorine, chlorine or bromine P represents 1, Z represents N, CH, or CCl, and wherein the compound of formula (I) can furthermore comprise an N-oxide and/or salt thereof, wherein


2. A mixture of compounds according to claim 1, in which Qy is Q62 and Q63, the ratio of a compound of the formula (I) in which Qy is Q62 to a compound of the formula (I) in which Qy is Q63 being 60:40 to 99:1.
 3. A mixture of compounds according to claim 1, in which Qy is Q58 and Q59, the ratio of a compound of the formula (I) in which Qy is Q58 to a compound of the formula (I) in which Qy is Q59 being 60:40 to 99:1.
 4. A process for preparing a compound according to claim 1, comprising (A) reacting an aniline of formula (II)

in which X represents O, optionally, with a carbonyl chloride of formula (III)

in the presence of an acid-binding agent; or (B) reacting an aniline of formula (II)

in which X represents O, optionally, with a carboxylic acid of the formula (IV)

in the presence of a condensing agent; or (C) for the synthesis of an anthranilamide of formula (I) in which R¹ represents hydrogen, optionally reacting a benzoxazinone of formula (V)

with an amine of the formula (VI)

in the presence of a diluent.
 5. A composition comprising at least one compound according to claim 1 and at least one salt of formula (XXIV)

in which D represents nitrogen or phosphorus, R¹⁰, R¹¹, R¹², R¹³, independently of one another represent hydrogen or in each case optionally substituted C₁-C₈-alkyl or mono- or polyunsaturated, optionally substituted C₁-C₈-alkylen where the substituents may be selected from the group consisting of halogen, nitro and, cyano, m represents 1, 2, 3 or 4, R¹⁴ represents an inorganic or organic anion.
 6. A composition comprising at least one compound according to claim 1 and at least one penetrant of formula (XXV) R-O—(-AO)_(V)-R′  (XXV) in which R represents straight-chain or branched alkyl having 4 to 20 carbon atoms R¹ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl, AO represents an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or represents a mixture of ethylene oxide and propylene oxide radicals or butylene oxide radicals and V represents a number from 2 to
 30. 7. An agrochemical composition comprising at least one compound according to claim 1 and at least one extender and/or surfactant.
 8. A process for producing an agrochemical composition comprising mixing at least one compound according to claim 1 with at least one extender and/or surfactant.
 9. Method for controlling animal pests comprising applying at least one compound according to of claim 1 to animal pests and/or phytopathogenic fungi and/or their habitat and/or seed.
 10. A compound according to claim 1, in which the compound has the following structure: 